Bright stock and heavy neutral production from resid deasphalting

ABSTRACT

Methods are provided for forming lubricant base stocks from feeds such as vacuum resid or other 510° C.+ feeds. A feed can be deasphalted and then catalytically and/or solvent processed to form lubricant base stocks, including bright stocks that are resistant to haze formation.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser.No. 62/271,543 filed Dec. 28, 2015, which is herein incorporated byreference in its entirety.

This application is related to five (5) other co-pending non-provisionalU.S. applications, filed on even date herewith, and identified by thefollowing Attorney Docket numbers and titles: 2016EM400 entitled “BrightStock Production From Low Severity Resid Deasphalting”; 2016EM401entitled “Bright Stock Production From Low Severity Resid Deasphalting”;2016EM404 entitled “Bright Stock Production From Deasphalted Oil”;2016EM402 entitled “Integrated Resid Deasphalting And Gasification” and2016EM403 entitled “Sequential Deasphalting For Base Stock Production”.Each of these co-pending US applications is hereby incorporated byreferences herein in their entirety.

FIELD

Systems and methods are provided for production of lubricant oil basestocks from deasphalted oils produced by deasphalting of residfractions.

BACKGROUND

Lubricant base stocks are one of the higher value products that can begenerated from a crude oil or crude oil fraction. The ability togenerate lubricant base stocks of a desired quality is often constrainedby the availability of a suitable feedstock. For example, mostconventional processes for lubricant base stock production invokestarting with a crude fraction that has not been previously processedunder severe conditions, such as a virgin gas oil fraction from a crudewith moderate to low levels of initial sulfur content.

In some situations, a deasphalted oil formed by propane desaphalting ofa vacuum resid can be used for additional lubricant base stockproduction. Deasphalted oils can potentially be suitable for productionof heavier base stocks, such as bright stocks. However, the severity ofpropane deasphalting required in order to make a suitable feed forlubricant base stock production typically results in a yield of onlyabout 30 wt % deasphalted oil relative to the vacuum resid feed.

U.S. Pat. No. 3,414,506 describes methods for making lubricating oils byhydrotreating pentane-alcohol-deasphalted short residue. The methodsinclude performing deasphalting on a vacuum resid fraction with adeasphalting solvent comprising a mixture of an alkane, such as pentane,and one or more short chain alcohols, such as methanol and isopropylalcohol. The deasphalted oil is then hydrotreated, followed by solventextraction to perform sufficient VI uplift to form lubricating oils.

U.S. Pat. No. 7,776,206 describes methods for catalytically processingresids and/or deasphalted oils to form bright stock. A resid-derivedstream, such as a deasphalted oil, is hydroprocessed to reduce thesulfur content to less than 1 wt % and reduce the nitrogen content toless than 0.5 wt %. The hydroprocessed stream is then fractionated toform a heavier fraction and a lighter fraction at a cut point between1150° F.-1300° F. (620° C.-705° C.). The lighter fraction is thencatalytically processed in various manners to form a bright stock.

SUMMARY

In various aspects, methods are provided for producing lubricant basestocks, such as bright stocks and wide cut heavy neutral base stocks,from deasphalted oils generated by deasphalting with C₃ and/or C₄deasphalting solvents. The deasphalted oil yield can be less than 50 wt% relative to the feed to deasphalting, or 40 wt % or less, or 35 wt %or less.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows an example of a configuration for processinga deasphalted oil to form a lubricant base stock.

FIG. 2 schematically shows another example of a configuration forprocessing a deasphalted oil to form a lubricant base stock.

FIG. 3 schematically shows another example of a configuration forprocessing a deasphalted oil to form a lubricant base stock.

FIG. 4 shows results from processing a pentane deasphalted oil atvarious levels of hydroprocessing severity.

FIG. 5 shows results from processing deasphalted oil in configurationswith various combinations of sour hydrocracking and sweet hydrocracking.

FIG. 6 schematically shows an example of a configuration for catalyticprocessing of deasphalted oil to form lubricant base stocks.

FIG. 7 shows properties of lubricant base stocks made from variouspropane deasphalted feeds and reference base stocks.

FIG. 8 shows properties of lubricant base stocks made from variousbutane deasphalted feeds.

FIG. 9 shows properties of lubricant base stocks made from variouspentane deasphalted feeds.

FIG. 10 shows properties of lubricant base stocks made from variouspentane deasphalted feeds.

FIG. 11 shows properties of a propane deasphalted oil.

FIG. 12 shows properties for hydroprocessed effluent fractions fromprocessing of a propane deasphalted oil.

DETAILED DESCRIPTION

All numerical values within the detailed description and the claimsherein are modified by “about” or “approximately” the indicated value,and take into account experimental error and variations that would beexpected by a person having ordinary skill in the art.

Overview

In various aspects, methods are provided for producing Group I and GroupII lubricant base stocks, including Group I and Group II bright stock,from deasphalted oils generated by low severity C₄₊ deasphalting. Lowseverity deasphalting as used herein refers to deasphalting underconditions that result in a high yield of deasphalted oil (and/or areduced amount of rejected asphalt or rock), such as a deasphalted oilyield of at least 50 wt % relative to the feed to deasphalting, or atleast 55 wt %, or at least 60 wt %, or at least 65 wt %, or at least 70wt %, or at least 75 wt %. The Group I base stocks (including brightstock) can be formed without performing a solvent extraction on thedeasphalted oil. The Group II base stocks (including bright stock) canbe formed using a combination of catalytic and solvent processing. Incontrast with conventional bright stock produced from deasphalted oilformed at low severity conditions, the Group I and Group II bright stockdescribed herein can be substantially free from haze after storage forextended periods of time. This haze free Group II bright stock cancorrespond to a bright stock with an unexpected composition.

In various additional aspects, methods are provided for catalyticprocessing of C₃ deasphalted oils to form Group II bright stock. FormingGroup II bright stock by catalytic processing can provide a bright stockwith unexpected compositional properties.

Conventionally, crude oils are often described as being composed of avariety of boiling ranges. Lower boiling range compounds in a crude oilcorrespond to naphtha or kerosene fuels. Intermediate boiling rangedistillate compounds can be used as diesel fuel or as lubricant basestocks. If any higher boiling range compounds are present in a crudeoil, such compounds are considered as residual or “resid” compounds,corresponding to the portion of a crude oil that is left over afterperforming atmospheric and/or vacuum distillation on the crude oil.

In some conventional processing schemes, a resid fraction can bedeasphalted, with the deasphalted oil used as part of a feed for forminglubricant base stocks. In conventional processing schemes a deasphaltedoil used as feed for forming lubricant base stocks is produced usingpropane deasphalting. This propane deasphalting corresponds to a “highseverity” deasphalting, as indicated by a typical yield of deasphaltedoil of about 40 wt % or less, often 30 wt % or less, relative to theinitial resid fraction. In a typical lubricant base stock productionprocess, the deasphalted oil can then be solvent extracted to reduce thearomatics content, followed by solvent dewaxing to form a base stock.The low yield of deasphalted oil is based in part on the inability ofconventional methods to produce lubricant base stocks from lowerseverity deasphalting that do not form haze over time.

In some aspects, it has been discovered that using a mixture ofcatalytic processing, such as hydrotreatment, and solvent processing,such as solvent dewaxing, can be used to produce lubricant base stocksfrom deasphalted oil while also producing base stocks that have littleor no tendency to form haze over extended periods of time. Thedeasphalted oil can be produced by deasphalting process that uses a C₄solvent, a C₅ solvent, a C₆₊ solvent, a mixture of two or more C₄₊solvents, or a mixture of two or more C₅₊ solvents. The deasphaltingprocess can further correspond to a process with a yield of deasphaltedoil of at least 50 wt % fora vacuum resid feed having a T10 distillationpoint (or optionally a T5 distillation point) of at least 510° C., or ayield of at least 60 wt %, or at least 65 wt %, or at least 70 wt %. Itis believed that the reduced haze formation is due in part to thereduced or minimized differential between the pour point and the cloudpoint for the base stocks and/or due in part to forming a bright stockwith a cloud point of −5° C. or less.

For production of Group I base stocks, a deasphalted oil can behydroprocessed (hydrotreated and/or hydrocracked) under conditionssufficient to achieve a desired viscosity index increase for resultingbase stock products. The hydroprocessed effluent can be fractionated toseparate lower boiling portions from a lubricant base stock boilingrange portion. The lubricant base stock boiling range portion can thenbe solvent dewaxed to produce a dewaxed effluent. The dewaxed effluentcan be separated to form a plurality of base stocks with a reducedtendency (such as no tendency) to form haze over time.

For production of Group II base stocks, in some aspects a deasphaltedoil can be hydroprocessed (hydrotreated and/or hydrocracked), so that˜700° F.+ (370° C.+) conversion is 10 wt % to 40 wt %. Thehydroprocessed effluent can be fractionated to separate lower boilingportions from a lubricant base stock boiling range portion. Thelubricant boiling range portion can then be hydrocracked, dewaxed, andhydrofinished to produce a catalytically dewaxed effluent. Optionallybut preferably, the lubricant boiling range portion can be underdewaxed,so that the wax content of the catalytically dewaxed heavier portion orpotential bright stock portion of the effluent is at least 6 wt %, or atleast 8 wt %, or at least 10 wt %. This underdewaxing can also besuitable for forming light or medium or heavy neutral lubricant basestocks that do not require further solvent upgrading to form haze freebase stocks. In this discussion, the heavier portion/potential brightstock portion can roughly correspond to a 538° C.+ portion of thedewaxed effluent. The catalytically dewaxed heavier portion of theeffluent can then be solvent dewaxed to form a solvent dewaxed effluent.The solvent dewaxed effluent can be separated to form a plurality ofbase stocks with a reduced tendency (such as no tendency) to form hazeover time, including at least a portion of a Group II bright stockproduct.

For production of Group II base stocks, in other aspects a deasphaltedoil can be hydroprocessed (hydrotreated and/or hydrocracked), so that370° C.+ conversion is at least 40 wt %, or at least 50 wt %. Thehydroprocessed effluent can be fractionated to separate lower boilingportions from a lubricant base stock boiling range portion. Thelubricant base stock boiling range portion can then be hydrocracked,dewaxed, and hydrofinished to produce a catalytically dewaxed effluent.The catalytically dewaxed effluent can then be solvent extracted to forma raffinate. The raffinate can be separated to form a plurality of basestocks with a reduced tendency (such as no tendency) to form haze overtime, including at least a portion of a Group II bright stock product.

In other aspects, it has been discovered that catalytic processing canbe used to produce Group II bright stock with unexpected compositionalproperties from C₃, C₄, C₅, and/or C₅₊ deasphalted oil. The deasphaltedoil can be hydrotreated to reduce the content of heteroatoms (such assulfur and nitrogen), followed by catalytic dewaxing under sweetconditions. Optionally, hydrocracking can be included as part of thesour hydrotreatment stage and/or as part of the sweet dewaxing stage.

In various aspects, a variety of combinations of catalytic and/orsolvent processing can be used to form lubricant base stocks, includingGroup II bright stock, from deasphalted oils. These combinationsinclude, but are not limited to:

a) Hydroprocessing of a deasphalted oil under sour conditions (i.e.,sulfur content of at least 500 wppm); separation of the hydroprocessedeffluent to form at least a lubricant boiling range fraction; andsolvent dewaxing of the lubricant boiling range fraction. In someaspects, the hydroprocessing of the deasphalted oil can correspond tohydrotreatment, hydrocracking, or a combination thereof.

b) Hydroprocessing of a deasphalted oil under sour conditions (i.e.,sulfur content of at least 500 wppm); separation of the hydroprocessedeffluent to form at least a lubricant boiling range fraction; andcatalytic dewaxing of the lubricant boiling range fraction under sweetconditions (i.e., 500 wppm or less sulfur). The catalytic dewaxing canoptionally correspond to catalytic dewaxing using a dewaxing catalystwith a pore size greater than 8.4 Angstroms. Optionally, the sweetprocessing conditions can further include hydrocracking, noble metalhydrotreatment, and/or hydrofinishing. The optional hydrocracking, noblemetal hydrotreatment, and/or hydrofinishing can occur prior to and/orafter or after catalytic dewaxing. For example, the order of catalyticprocessing under sweet processing conditions can be noble metalhydrotreating followed by hydrocracking followed by catalytic dewaxing.

c) The process of b) above, followed by performing an additionalseparation on at least a portion of the catalytically dewaxed effluent.The additional separation can correspond to solvent dewaxing, solventextraction (such as solvent extraction with furfural orn-methylpyrollidone), a physical separation such as ultracentrifugation,or a combination thereof.

d) The process of a) above, followed by catalytic dewaxing (sweetconditions) of at least a portion of the solvent dewaxed product.Optionally, the sweet processing conditions can further includehydrotreating (such as noble metal hydrotreating), hydrocracking and/orhydrofinishing. The additional sweet hydroprocessing can be performedprior to and/or after the catalytic dewaxing.

Group I base stocks or base oils are defined as base stocks with lessthan 90 wt % saturated molecules and/or at least 0.03 wt % sulfurcontent. Group I base stocks also have a viscosity index (VI) of atleast 80 but less than 120. Group II base stocks or base oils contain atleast 90 wt % saturated molecules and less than 0.03 wt % sulfur. GroupII base stocks also have a viscosity index of at least 80 but less than120. Group III base stocks or base oils contain at least 90 wt %saturated molecules and less than 0.03 wt % sulfur, with a viscosityindex of at least 120.

In some aspects, a Group III base stock as described herein maycorrespond to a Group III+ base stock. Although a generally accepteddefinition is not available, a Group III+ base stock can generallycorrespond to a base stock that satisfies the requirements for a GroupIII base stock while also having at least one property that is enhancedrelative to a Group III specification. The enhanced property cancorrespond to, for example, having a viscosity index that issubstantially greater than the required specification of 120, such as aGroup III base stock having a VI of at least 130, or at least 135, or atleast 140. Similarly, in some aspects, a Group II base stock asdescribed herein may correspond to a Group II+ base stock. Although agenerally accepted definition is not available, a Group II+ base stockcan generally correspond to a base stock that satisfies the requirementsfor a Group II base stock while also having at least one property thatis enhanced relative to a Group II specification. The enhanced propertycan correspond to, for example, having a viscosity index that issubstantially greater than the required specification of 80, such as aGroup II base stock having a VI of at least 103, or at least 108, or atleast 113.

In the discussion below, a stage can correspond to a single reactor or aplurality of reactors. Optionally, multiple parallel reactors can beused to perform one or more of the processes, or multiple parallelreactors can be used for all processes in a stage. Each stage and/orreactor can include one or more catalyst beds containing hydroprocessingcatalyst. Note that a “bed” of catalyst in the discussion below canrefer to a partial physical catalyst bed. For example, a catalyst bedwithin a reactor could be filled partially with a hydrocracking catalystand partially with a dewaxing catalyst. For convenience in description,even though the two catalysts may be stacked together in a singlecatalyst bed, the hydrocracking catalyst and dewaxing catalyst can eachbe referred to conceptually as separate catalyst beds.

In this discussion, conditions may be provided for various types ofhydroprocessing of feeds or effluents. Examples of hydroprocessing caninclude, but are not limited to, one or more of hydrotreating,hydrocracking, catalytic dewaxing, and hydrofinishing/aromaticsaturation. Such hydroprocessing conditions can be controlled to havedesired values for the conditions (e.g., temperature, pressure, treatgas rate) by using at least one controller, such as a plurality ofcontrollers, to control one or more of the hydroprocessing conditions.In some aspects, for a given type of hydroprocessing, at least onecontroller can be associated with each type of hydroprocessingcondition. In some aspects, one or more of the hydroprocessingconditions can be controlled by an associated controller. Examples ofstructures that can be controlled by a controller can include, but arenot limited to, valves that control a flow rate, a pressure, or acombination thereof; heat exchangers and/or heaters that control atemperature; and one or more flow meters and one or more associatedvalves that control relative flow rates of at least two flows. Suchcontrollers can optionally include a controller feedback loop includingat least a processor, a detector for detecting a value of a controlvariable (e.g., temperature, pressure, flow rate, and a processor outputfor controlling the value of a manipulated variable (e.g., changing theposition of a valve, increasing or decreasing the duty cycle and/ortemperature for a heater). Optionally, at least one hydroprocessingcondition for a given type of hydroprocessing may not have an associatedcontroller.

In this discussion, unless otherwise specified a lubricant boiling rangefraction corresponds to a fraction having an initial boiling point oralternatively a T5 boiling point of at least about 370° C. (˜700° F.). Adistillate fuel boiling range fraction, such as a diesel productfraction, corresponds to a fraction having a boiling range from about193° C. (375° F.) to about 370° C. (˜700° F.). Thus, distillate fuelboiling range fractions (such as distillate fuel product fractions) canhave initial boiling points (or alternatively T5 boiling points) of atleast about 193° C. and final boiling points (or alternatively T95boiling points) of about 370° C. or less. A naphtha boiling rangefraction corresponds to a fraction having a boiling range from about 36°C. (122° F.) to about 193° C. (375° F.) to about 370° C. (˜700° F.).Thus, naphtha fuel product fractions can have initial boiling points (oralternatively T5 boiling points) of at least about 36° C. and finalboiling points (or alternatively T95 boiling points) of about 193° C. orless. It is noted that 36° C. roughly corresponds to a boiling point forthe various isomers of a C₅ alkane. A fuels boiling range fraction cancorrespond to a distillate fuel boiling range fraction, a naphthaboiling range fraction, or a fraction that includes both distillate fuelboiling range and naphtha boiling range components. Light ends aredefined as products with boiling points below about 36° C., whichinclude various C 1-C₄ compounds. When determining a boiling point or aboiling range for a feed or product fraction, an appropriate ASTM testmethod can be used, such as the procedures described in ASTM D2887,D2892, and/or D86. Preferably, ASTM D2887 should be used unless a sampleis not appropriate for characterization based on ASTM D2887. Forexample, for samples that will not completely elute from achromatographic column, ASTM D7169 can be used.

Feedstocks

In various aspects, at least a portion of a feedstock for processing asdescribed herein can correspond to a vacuum resid fraction or anothertype 950° F.+ (510° C.+) or 1000° F.+ (538° C.+) fraction. Anotherexample of a method for forming a 950° F.+ (510° C.+) or 1000° F+ (538°C.+) fraction is to perform a high temperature flash separation. The950° F.+ (510° C.+) or 1000° F.+ (538° C.+) fraction formed from thehigh temperature flash can be processed in a manner similar to a vacuumresid.

A vacuum resid fraction or a 950° F.+ (510° C.+) fraction formed byanother process (such as a flash fractionation bottoms or a bitumenfraction) can be deasphalted at low severity to form a deasphalted oil.Optionally, the feedstock can also include a portion of a conventionalfeed for lubricant base stock production, such as a vacuum gas oil.

A vacuum resid (or other 510° C.+) fraction can correspond to a fractionwith a T5 distillation point (ASTM D2892, or ASTM D7169 if the fractionwill not completely elute from a chromatographic system) of at leastabout 900° F. (482° C.), or at least 950° F. (510° C.), or at least1000° F. (538° C.). Alternatively, a vacuum resid fraction can becharacterized based on a T10 distillation point (ASTM D2892/D7169) of atleast about 900° F. (482° C.), or at least 950° F. (510° C.), or atleast 1000° F. (538° C.).

Resid (or other 510° C.+) fractions can be high in metals. For example,a resid fraction can be high in total nickel, vanadium and ironcontents. In an aspect, a resid fraction can contain at least 0.00005grams of Ni/V/Fe (50 wppm) or at least 0.0002 grams of Ni/V/Fe (200wppm) per gram of resid, on a total elemental basis of nickel, vanadiumand iron. In other aspects, the heavy oil can contain at least 500 wpmof nickel, vanadium, and iron, such as up to 1000 wppm or more.

Contaminants such as nitrogen and sulfur are typically found in resid(or other 510° C.+) fractions, often in organically-hound form. Nitrogencontent can range from about 50 wppm to about 10,000 wppm elementalnitrogen or more, based on total weight of the resid fraction. Sulfurcontent can range from 500 wppm to 100,000 wppm elemental sulfur ormore, based on total weight of the resid fraction, or from 1000 wppm to50,000 wppm, or from 1000 wppm to 30,000 wppm.

Still another method for characterizing a resid (or other 510° C.+)fraction is based on the Conradson carbon residue (CCR) of thefeedstock. The Conradson carbon residue of a resid fraction can be atleast about 5 wt %, such as at least about 10 wt % or at least about 20wt %. Additionally or alternately, the Conradson carbon residue of aresid fraction can be about 50 wt % or less, such as about 40 wt % orless or about 30 wt % or less.

In some aspects, a vacuum gas oil fraction can be co-processed with adeasphalted oil. The vacuum gas oil can be combined with the deasphaltedoil in various amounts ranging from 20 parts (by weight) deasphalted oilto 1 part vacuum gas oil (i.e., 20:1) to 1 part deasphalted oil to 1part vacuum gas oil, in some aspects, the ratio of deasphalted oil tovacuum gas oil can be at least 1:1 by weight, or at least 1.5:1, or atleast 2:1. Typical (vacuum) gas oil fractions can include, for example,fractions with a T5 distillation point to T95 distillation point of 650°F. (343° C.)-1050° F. (566° C.), or 650° F. (343° C.)-1000° F. (538°C.), or 650° F. (343° C.)-950° F. (510° C.), or 650° F. (343° C.)-900°F. (482° C.), or ˜700° F. (370° C.)-1050° F. (566° C.), or ˜700° F.(370° C.)-1000° F. (538° C.), or ˜700° F. (370° C.)-950° F. (510° C.),or ˜700° F. (370° C.)-900° F. (482° C.), or 750° F. (399° C.)-1050° F.(566° C.), or 750° F. (399° C.)-1000° F. (538° C.), or 750° F. (399°C.)-950° F. (510° C.), or 750° F. (399° C.)-900° F. (482° C.). Forexample a suitable vacuum gas oil fraction can have a TS distillationpoint of at least 343° C. and a T95 distillation point of 566° C. orless; or a T10 distillation point of at least 343° C. and a T90distillation point of 566° C. or less; or a T5 distillation point of atleast 370° C. and a T95 distillation point of 566° C. or less; or a T5distillation point of at least 343° C. and a T95 distillation point of538° C. or less.

Solvent Deasphalting

Solvent deasphalting is a solvent extraction process. In sonic aspects,suitable solvents for methods as described herein include alkanes orother hydrocarbons (such as alkenes) containing 4 to 7 carbons permolecule. Examples of suitable solvents include n-butane, isobutane,n-pentane, C₄₊ alkanes, C₅₊ alkanes, C₄₊ hydrocarbons, and C₅₊hydrocarbons. In other aspects, suitable solvents can include C₃hydrocarbons, such as propane. In such other aspects, examples ofsuitable solvents include propane, n-butane, isobutane, n-pentane, C₃₊alkanes, C₄₊ alkanes, C₅₊ alkanes, C₃₊ hydrocarbons, C₄₊ hydrocarbons,and C₅₊ hydrocarbons.

In this discussion, a solvent comprising C_(n) (hydrocarbons) is definedas a solvent composed of at least 80 wt % of alkanes (hydrocarbons)having n carbon atoms, or at least 85 wt %, or at least 90 wt %, or atleast 95 wt %, or at least 98 wt %. Similarly, a solvent comprisingC_(n+) (hydrocarbons) is defined as a solvent composed of at least 80 wt% of alkanes (hydrocarbons) having n or more carbon atoms, or at least85 wt %, or at least 90 wt %, or at least 95 wt %, or at least 98 wt %.

In this discussion, a solvent comprising C_(n) alkanes (hydrocarbons) isdefined to include the situation where the solvent corresponds to asingle alkane (hydrocarbon) containing n carbon atoms (for example, n=3,4, 5, 6, 7) as well as the situations where the solvent is composed of amixture of alkanes (hydrocarbons) containing n carbon atoms. Similarly,a solvent comprising C_(n+) alkanes (hydrocarbons) is defined to includethe situation where the solvent corresponds to a single alkane(hydrocarbon) containing n or more carbon atoms (for example, n=3, 4, 5,6, 7) as well as the situations where the solvent corresponds to amixture of alkanes (hydrocarbons) containing n or more carbon atoms.Thus, a solvent comprising C₄₊ alkanes can correspond to a solventincluding n-butane; a solvent include n-butane and isobutane; a solventcorresponding to a mixture of one or more butane isomers and one or morepentane isomers; or any other convenient combination of alkanescontaining 4 or more carbon atoms. Similarly, a solvent comprising C₅₊alkanes (hydrocarbons) is defined to include a solvent corresponding toa single alkane (hydrocarbon) or a solvent corresponding to a mixture ofalkanes (hydrocarbons) that contain 5 or more carbon atoms.Alternatively, other types of solvents may also be suitable, such assupercritical fluids. In various aspects, the solvent for solventdeasphalting can consist essentially of hydrocarbons, so that at least98 wt % or at least 99 wt % of the solvent corresponds to compoundscontaining only carbon and hydrogen. In aspects where the deasphaltingsolvent corresponds to a C₄₊ deasphalting solvent, the C₄₊ deasphaltingsolvent can include less than 15 wt % propane and/or other C₃hydrocarbons, or less than 10 wt %, or less than 5 wt %, or the C₄₊deasphalting solvent can be substantially free of propane and/or otherC₃ hydrocarbons (less than 1 wt %). In aspects where the deasphaltingsolvent corresponds to a C₅₊ deasphalting solvent, the C₅₊ deasphaltingsolvent can include less than 15 wt % propane, butane and/or other C₃-C₄hydrocarbons, or less than 10 wt %, or less than 5 wt %, or the C₅₊deasphalting solvent can be substantially free of propane, butane,and/or other C₃-C₄ hydrocarbons (less than 1 wt %), in aspects where thedeasphalting solvent corresponds to a C₃₊ deasphalting solvent, the C₃₊deasphalting solvent can include less than 10 wt % ethane and/or otherC₂ hydrocarbons, or less than 5 wt %, or the C₃₊ deasphalting solventcan be substantially free of ethane and/or other C₂ hydrocarbons (lessthan 1 wt %).

Deasphalting of heavy hydrocarbons, such as vacuum resids, is known inthe art and practiced commercially. A deasphalting process typicallycorresponds to contacting a heavy hydrocarbon with an alkane solvent(propane, butane, pentane, hexane, heptane etc. and their isomers),either in pure form or as mixtures, to produce two types of productstreams. One type of product stream can be a deasphalted oil extractedby the alkane, which is further separated to produce deasphalted oilstream. A second type of product stream can be a residual portion of thefeed not soluble in the solvent, often referred to as rock or asphaltenefraction. The deasphalted oil fraction can be further processed intomake fuels or lubricants. The rock fraction can be further used as blendcomponent to produce asphalt, fuel oil, and/or other products. The rockfraction can also be used as feed to gasification processes such aspartial oxidation, fluid bed combustion or coking processes. The rockcan be delivered to these processes as a liquid (with or withoutadditional components) or solid (either as pellets or lumps).

During solvent deasphalting, a resid boiling range feed (optionally alsoincluding a portion of a vacuum gas oil feed) can be mixed with asolvent. Portions of the feed that are soluble in the solvent are thenextracted, leaving behind a residue with little or no solubility in thesolvent. The portion of the deasphalted feedstock that is extracted withthe solvent is often referred to as deasphalted oil. Typical solventdeasphalting conditions include mixing a feedstock fraction with asolvent in a weight ratio of from about 1:2 to about 1: 10, such asabout 1:8 or less. Typical solvent deasphalting temperatures range from40° C. to 200° C., or 40° C. to 150° C., depending on the nature of thefeed and the solvent. The pressure during solvent deasphalting can befrom about 50 psig (345 kPag) to about 500 psig (3447 kPag).

It is noted that the above solvent deasphalting conditions represent ageneral range, and the conditions will vary depending on the feed. Forexample, under typical deasphalting conditions, increasing thetemperature can tend to reduce the yield while increasing the quality ofthe resulting deasphalted oil. Under typical deasphalting conditions,increasing the molecular weight of the solvent can tend to increase theyield while reducing the quality of the resulting deasphalted oil, asadditional compounds within a resid fraction may be soluble in a solventcomposed of higher molecular weight hydrocarbons. Under typicaldeasphalting conditions, increasing the amount of solvent can tend toincrease the yield of the resulting deasphalted oil. As understood bythose of skill in the art, the conditions for a particular feed can beselected based on the resulting yield of deasphalted oil from solventdeasphalting. In aspects where a C₃ deasphalting solvent is used, theyield from solvent deasphalting can be 40 wt % or less. In some aspects.C₄ deasphalting can be performed with a yield of deasphalted oil of 50wt % or less, or 40 wt % or less. In various aspects, the yield ofdeasphalted oil from solvent deasphalting with a C₄₊ solvent can be atleast 50 wt % relative to the weight of the feed to deasphalting, or atleast 55 wt %, or at least 60 wt % or at least 65 wt %, or at least 70wt %. In aspects where the feed to deasphalting includes a vacuum gasoil portion, the yield from solvent deasphalting can be characterizedbased on a yield by weight of a 950° F.+ (510° C.) portion of thedeasphalted oil relative to the weight of a 510° C.+ portion of thefeed. In such aspects where a C₄₊ solvent is used, the yield of 510° C.+deasphalted oil from solvent deasphalting can be at least 40 wt %relative to the weight of the 510° C.+ portion of the feed todeasphalting, or at least 50 wt %, or at least 55 wt %, or at least 60wt % or at least 65 wt %, or at least 70 wt %. In such aspects where aC₄₊ solvent is used, the yield of 510° C.+ deasphalted oil from solventdeasphalting can be 50 wt % or less relative to the weight of the 510°C.+ portion of the feed to deasphalting, or 40 wt % or less, or 35 wt %or less.

Hydrotreating and Hydrocracking

After deasphalting, the deasphalted oil (and any additional fractionscombined with the deasphalted oil) can undergo further processing toform lubricant base stocks. This can include hydrotreatment and/orhydrocracking to remove heteroatoms to desired levels, reduce ConradsonCarbon content, and/or provide viscosity index (VI) uplift. Depending onthe aspect, a deasphalted oil can be hydroprocessed by hydrotreating,hydrocracking, or hydrotreating and hydrocracking.

The deasphalted oil can be hydrotreated and/or hydrocracked with littleor no solvent extraction being performed prior to and/or after thedeasphalting. As a result, the deasphalted oil feed for hydrotreatmentand/or hydrocracking can have a substantial aromatics content, invarious aspects, the aromatics content of the deasphalted oil feed canbe at least 50 wt %, or at least 55 wt %, or at least 60 wt %, or atleast 65 wt %, or at least 70 wt %, or at least 75 wt %, such as up to90 wt % or more. Additionally or alternately, the saturates content ofthe deasphalted oil feed can be 50 wt % or less, or 45 wt % or less, or40 wt % or less, or 35 wt % or less, or 30 wt % or less, or 25 wt % orless, such as down to 10 wt % or less. In this discussion and the claimsbelow, the aromatics content and/or the saturates content of a fractioncan be determined based on ASTM D7419.

The reaction conditions during demetallization and/or hydrotreatmentand/or hydrocracking of the deasphalted oil (and optional vacuum gas oilco-feed) can be selected to generate a desired level of conversion of afeed. Any convenient type of reactor, such as fixed bed (for exampletrickle bed) reactors can be used. Conversion of the feed can be definedin terms of conversion of molecules that boil above a temperaturethreshold to molecules below that threshold. The conversion temperaturecan be any convenient temperature, such as ˜700° F. (370° C.) or 1050°F. (566° C.). The amount of conversion can correspond to the totalconversion of molecules within the combined hydrotreatment andhydrocracking stages for the deasphalted oil. Suitable amounts ofconversion of molecules boiling above 1050° F. (566° C.) to moleculesboiling below 566° C. include 30 wt % to 90 wt % conversion relative to566° C., or 30 wt % to 80 wt %, or 30 wt % to 70 wt %, or 40 wt % to 90wt %, or 40 wt % to 80 wt %, or 40 wt % to 70 wt %, or 50 wt % to 90 wt%, or 50 wt % to 80 wt %, or 50 wt % to 70 wt %. In particular, theamount of conversion relative to 566° C. can be 30 wt % to 90 wt %, or30 wt % to 70 wt %, or 50 wt % to 90 wt %. Additionally or alternately,suitable amounts of conversion of molecules boiling above ˜700° F. (370°C.) to molecules boiling below 370° C. include 10 wt % to 70 wt %conversion relative to 370° C., or 10 wt % to 60 wt %, or 10 wt % to 50wt %, or 20 wt % to 70 wt %, or 20 wt % to 60 wt %, or 20 wt % to 50 wt%, or 30 wt % to 70 wt %, or 30 wt % to 60 wt %, or 30 wt % to 50 wt %.In particular, the amount of conversion relative to 370° C. can be 10 wt% to 70 wt %, or 20 wt % to 50 wt %, or 30 wt % to 60 wt %.

The hydroprocessed deasphalted oil can also be characterized based onthe product quality. After hydroprocessing (hydrotreating and/orhydrocracking), the hydroprocessed deasphalted oil can have a sulfurcontent of 200 wppm or less, or 100 wppm or less, or 50 wppm or less(such as down to ˜0 wppm). Additionally or alternately, thehydroprocessed deasphalted oil can have a nitrogen content of 200 wppmor less, or 100 wppm or less, or 50 wppm or less (such as down to ˜0wppm). Additionally or alternately, the hydroprocessed deasphalted oilcan have a Conradson Carbon residue content of 1.5 wt % or less, or 1.0wt % or less, or 0.7 wt % or less, or 0.1 wt % or less, or 0.02 wt % orless (such as down to ˜0 wt %). Conradson Carbon residue content can bedetermined according to ASTM D4530.

In various aspects, a feed can initially be exposed to a demetallizationcatalyst prior to exposing the feed to a hydrotreating catalyst.Deasphalted oils can have metals concentrations (Ni+V+Fe) on the orderof 10-100 wppm. Exposing a conventional hydrotreating catalyst to a feedhaving a metals content of 10 wpm or more can lead to catalystdeactivation at a faster rate than may desirable in a commercialsetting. Exposing a metal containing feed to a demetallization catalystprior to the hydrotreating catalyst can allow at least a portion of themetals to be removed by the demetallization catalyst, which can reduceor minimize the deactivation of the hydrotreating catalyst and/or othersubsequent catalysts in the process flow. Commercially availabledemetallization catalysts can be suitable, such as large pore amorphousoxide catalysts that may optionally include Group VI and/or Group VIIInon-noble metals to provide some hydrogenation activity.

In various aspects, the deasphalted oil can be exposed to ahydrotreating catalyst under effective hydrotreating conditions. Thecatalysts used can include conventional hydroprocessing catalysts, suchas those comprising at least one Group VIII non-noble metal (Columns8-10 of IUPAC periodic table), preferably Fe, Co, and/or Ni, such as Coand/or Ni; and at least one Group VI metal (Column 6 of IUPAC periodictable), preferably Mo and/or W. Such hydroprocessing catalystsoptionally include transition metal sulfides that are impregnated ordispersed on a refractory support or carrier such as alumina and/orsilica. The support or carrier itself typically has nosignificant/measurable catalytic activity. Substantially carrier- orsupport-free catalysts, commonly referred to as bulk catalysts,generally have higher volumetric activities than their supportedcounterparts.

The catalysts can either be in bulk form or in supported form. Inaddition to alumina and/or silica, other suitable support/carriermaterials can include, but are not limited to, zeolites, titania,silica-titania, and titania-alumina. Suitable aluminas are porousaluminas such as gamma or eta having average pore sizes from 50 to 200Å, or 75 to 150 Å; a surface area from 100 to 300 m²/g, or 150 to 250m²/g; and a pore volume of from 0.25 to 1.0 cm³/g, or 0.35 to 0.8 cm³/g.More generally, any convenient size, shape, and/or pore sizedistribution for a catalyst suitable for hydrotreatment of a distillate(including lubricant base stock) boiling range feed in a conventionalmanner may be used. Preferably, the support or carrier material is anamorphous support, such as a refractory oxide. Preferably, the supportor carrier material can be free or substantially free of the presence ofmolecular sieve, where substantially free of molecular sieve is definedas having a content of molecular sieve of less than about 0.01 wt %.

The at least one Group VIII non-noble metal, in oxide form, cantypically be present in an amount ranging from about 2 wt % to about 40wt %, preferably from about 4 wt % to about 15 wt %. The at least oneGroup VI metal, in oxide form, can typically be present in an amountranging from about 2 wt % to about 70 wt %, preferably for supportedcatalysts from about 6 wt % to about 40 wt % or from about 10 wt % toabout 30 wt %. These weight percents are based on the total weight ofthe catalyst. Suitable metal catalysts include cobalt/molybdenum (1-10%Co as oxide, 10-40% Mo as oxide), nickel/molybdenum (1-10% Ni as oxide,10-40% Co as oxide), or nickel/tungsten (1-10% Ni as oxide, 10-40% W asoxide) on alumina, silica, silica-alumina, or titania.

The hydrotreatment is carried out in the presence of hydrogen. Ahydrogen stream is, therefore, fed or injected into a vessel or reactionzone or hydroprocessing zone in which the hydroprocessing catalyst islocated. Hydrogen, which is contained in a hydrogen “treat gas,” isprovided to the reaction zone. Treat gas, as referred to in thisinvention, can be either pure hydrogen or a hydrogen-containing gas,which is a gas stream containing hydrogen in an amount that issufficient for the intended reaction(s), optionally including one ormore other gasses (e.g., nitrogen and light hydrocarbons such asmethane). The treat gas stream introduced into a reaction stage willpreferably contain at least about 50 vol. % and more preferably at leastabout 75 vol. % hydrogen. Optionally, the hydrogen treat gas can besubstantially free (less than 1 vol %) of impurities such as H₂S and NH₃and/or such impurities can be substantially removed from a treat gasprior to use.

Hydrogen can be supplied at a rate of from about 100 SCF/B (standardcubic feet of hydrogen per barrel of feed) (17 Nm³/m³) to about 10000SCF/B (1700 Nm³/m³). Preferably, the hydrogen is provided in a range offrom about 200 SCF/B (34 Nm³/m³) to about 2500 SCF/B (420 Nm³/m³).Hydrogen can be supplied co-currently with the input feed to thehydrotreatment reactor and/or reaction zone or separately via a separategas conduit to the hydrotreatment zone.

Hydrotreating conditions can include temperatures of 200° C. to 450° C.,or 315° C. to 425° C.; pressures of 250 psig (1.8 MPag) to 5000 psig(34.6 MPag) or 300 psig (2.1 MPag) to 3000 psig (20.8 MPag); liquidhourly space velocities (LHSV) of 0.1 hr⁻¹ to 10 hr⁻¹; and hydrogentreat rates of 200 scf/B (35.6 m³/m³) to 10,000 scf/B (1781 m³/m³), or500 (89 m³/m³) to 10.000 scf/B (1781 m³/m³).

In various aspects, the deasphalted oil can be exposed to ahydrocracking catalyst under effective hydrocracking conditions.Hydrocracking catalysts typically contain sulfided base metals on acidicsupports, such as amorphous silica alumina, cracking zeolites such asUSY, or acidified alumina. Often these acidic supports are mixed orbound with other metal oxides such as alumina, titania or silica.Examples of suitable acidic supports include acidic molecular sieves,such as zeolites or silicoaluminophophates. One example of suitablezeolite is USY, such as a USY zeolite with cell size of 24.30 Angstromsor less. Additionally or alternately, the catalyst can be a low aciditymolecular sieve, such as a USY zeolite with a Si to Al ratio of at leastabout 20, and preferably at least about 40 or 50. ZSM-48, such as ZSM-48with a SiO₂ to Al₂O₃ ratio of about 110 or less, such as about 90 orless, is another example of a potentially suitable hydrocrackingcatalyst. Still another option is to use a combination of USY andZSM-48. Still other options include using one or more of zeolite Beta,ZSM-5, ZSM-35, or ZSM-23, either alone or in combination with a USYcatalyst. Non-limiting examples of metals for hydrocracking catalystsinclude metals or combinations of metals that include at least one GroupVIII metal, such as nickel, nickel-cobalt-molybdenum, cobalt-molybdenum,nickel-tungsten, nickel-molybdenum, and/or nickel-molybdenum-tungsten.Additionally or alternately, hydrocracking catalysts with noble metalscan also be used. Non-limiting examples of noble metal catalysts includethose based on platinum and/or palladium. Support materials which may beused for both the noble and non-noble metal catalysts can comprise arefractory oxide material such as alumina, silica, alumina-silica,kieselguhr, diatomaceous earth, magnesia, zirconia, or combinationsthereof, with alumina, silica, alumina-silica being the most common (andpreferred, in one embodiment).

When only one hydrogenation metal is present on a hydrocrackingcatalyst, the amount of that hydrogenation metal can be at least about0.1 wt % based on the total weight of the catalyst, for example at leastabout 0.5 wt % or at least about 0.6 wt %. Additionally or alternatelywhen only one hydrogenation metal is present, the amount of thathydrogenation metal can be about 5.0 wt % or less based on the totalweight of the catalyst, for example about 3.5 wt % or less, about 2.5 wt% or less, about 1.5 wt % or less, about 1.0 wt % or less, about 0.9 wt% or less, about 0.75 wt % or less, or about 0.6 wt % or less. Furtheradditionally or alternately when more than one hydrogenation metal ispresent, the collective amount of hydrogenation metals can be at leastabout 0.1 wt % based on the total weight of the catalyst, for example atleast about 0.25 wt %, at least about 0.5 wt %, at least about 0.6 wt %,at least about 0.75 wt %, or at least about 1 wt %. Still furtheradditionally or alternately when more than one hydrogenation metal ispresent, the collective amount of hydrogenation metals can be about 35wt % or less based on the total weight of the catalyst, for exampleabout 30 wt % or less, about 25 wt % or less, about 20 wt % or less,about 15 wt % or less, about 10 wt % or less, or about 5 wt % or less.In embodiments wherein the supported metal comprises a noble metal, theamount of noble metal(s) is typically less than about 2 wt %, forexample less than about 1 wt %, about 0.9 wt % or less, about 0.75 wt orless, or about 0.6 wt % or less. It is noted that hydrocracking undersour conditions is typically performed using a base metal (or metals) asthe hydrogenation metal.

In various aspects, the conditions selected for hydrocracking forlubricant base stock production can depend on the desired level ofconversion, the level of contaminants in the input feed to thehydrocracking stage, and potentially other factors. For example,hydrocracking conditions in a single stage, or in the first stage and/orthe second stage of a multi-stage system, can be selected to achieve adesired level of conversion in the reaction system. Hydrocrackingconditions can be referred to as sour conditions or sweet conditions,depending on the level of sulfur and/or nitrogen present within a feed.For example, a feed with 100 wppm or less of sulfur and 50 wppm or lessof nitrogen, preferably less than 25 wppm sulfur and/or less than 10wppm of nitrogen, represent a feed for hydrocracking under sweetconditions. In various aspects, hydrocracking can be performed on athermally cracked resid, such as a deasphalted oil derived from athermally cracked resid. In some aspects, such as aspects where anoptional hydrotreating step is used prior to hydrocracking, thethermally cracked resid may correspond to a sweet feed. In otheraspects, the thermally cracked resid may represent a feed forhydrocracking under sour conditions.

A hydrocracking process under sour conditions can be carried out attemperatures of about 550° F. (288° C.) to about 840° F. (449° C.),hydrogen partial pressures of from about 1500 psig to about 5000 psig(10.3 MPag to 34.6 MPag), liquid hourly space velocities of from 0.05h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to 1781m³/m³ (200 SCF/B to 10,000 SCF/B). In other embodiments, the conditionscan include temperatures in the range of about 600° F. (343° C.) toabout 815° F. (435° C.), hydrogen partial pressures of from about 1500)psig to about 3000 psig (10.3 MPag-20.9 MPag), and hydrogen treat gasrates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000SCF/B). The LHSV can be from about 0.25 h⁻¹ to about 50 h⁻¹, or fromabout 0.5 h⁻¹ to about 20 h⁻¹, preferably from about 1.0 h⁻¹ to about4.0 h⁻¹.

In some aspects, a portion of the hydrocracking catalyst can becontained in a second reactor stage. In such aspects, a first reactionstage of the hydroprocessing reaction system can include one or morehydrotreating and/or hydrocracking catalysts. The conditions in thefirst reaction stage can be suitable for reducing the sulfur and/ornitrogen content of the feedstock. A separator can then be used inbetween the first and second stages of the reaction system to remove gasphase sulfur and nitrogen contaminants. One option for the separator isto simply perform a gas-liquid separation to remove contaminant. Anotheroption is to use a separator such as a flash separator that can performa separation at a higher temperature. Such a high temperature separatorcan be used, for example, to separate the feed into a portion boilingbelow a temperature cut point, such as about 350° F. (177° C.) or about400° F. (204° C.), and a portion boiling above the temperature cutpoint. In this type of separation, the naphtha boiling range portion ofthe effluent from the first reaction stage can also be removed, thusreducing the volume of effluent that is processed in the second or othersubsequent stages. Of course, any low boiling contaminants in theeffluent from the first stage would also be separated into the portionboiling below the temperature cut point. If sufficient contaminantremoval is performed in the first stage, the second stage can beoperated as a “sweet” or low contaminant stage.

Still another option can be to use a separator between the first andsecond stages of the hydroprocessing reaction system that can alsoperform at least a partial fractionation of the effluent from the firststage. In this type of aspect, the effluent from the firsthydroprocessing stage can be separated into at least a portion boilingbelow the distillate (such as diesel) fuel range, a portion boiling inthe distillate fuel range, and a portion boiling above the distillatefuel range. The distillate fuel range can be defined based on aconventional diesel boiling range, such as having a lower end cut pointtemperature of at least about 350° F. (177° C.) or at least about 400°F. (204° C.) to having an upper end cut point temperature of about 700°F. (371° C.) or less or 650° F. (343° C.) or less. Optionally, thedistillate fuel range can be extended to include additional kerosene,such as by selecting a lower end cut point temperature of at least about300° F. (149° C.).

In aspects where the inter-stage separator is also used to produce adistillate fuel fraction, the portion boiling below the distillate fuelfraction includes, naphtha boiling range molecules, light ends, andcontaminants such as H₂S. These different products can be separated fromeach other in any convenient manner. Similarly, one or more distillatefuel fractions can be formed, if desired, from the distillate boilingrange fraction. The portion boiling above the distillate fuel rangerepresents the potential lubricant base stocks. In such aspects, theportion boiling above the distillate fuel range is subjected to furtherhydroprocessing in a second hydroprocessing stage.

A hydrocracking process under sweet conditions can be performed underconditions similar to those used for a sour hydrocracking process, orthe conditions can be different. In an embodiment, the conditions in asweet hydrocracking stage can have less severe conditions than ahydrocracking process in a sour stage. Suitable hydrocracking conditionsfor a non-sour stage can include, but are not limited to, conditionssimilar to a first or sour stage. Suitable hydrocracking conditions caninclude temperatures of about 500° F. (260° C.) to about 840° F. (449°C.), hydrogen partial pressures of from about 1500 psig to about 5000psig (10.3 MPag to 34.6 MPag), liquid hourly space velocities of from0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates of from 35.6 m³/m³ to1781 m³/m³ (200 SCF/B to 10,000 SCF/B. In other embodiments, theconditions can include temperatures in the range of about 600° F. (343°C.) to about 815° F. (435° C.), hydrogen partial pressures of from about1500 psig to about 3000 psig (10.3 MPag-20.9 MPag), and hydrogen treatgas rates of from about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to6000 SCF/B). The LHSV can be from about 0.25 h⁻¹ to about 50 h⁻¹, orfrom about 0.5 h⁻¹ to about 20 h⁻¹, preferably from about 1.0 h⁻¹ toabout 4.0 h⁻¹.

In still another aspect, the same conditions can be used forhydrotreating and hydrocracking beds or stages, such as usinghydrotreating conditions for both or using hydrocracking conditions forboth. In yet another embodiment, the pressure for the hydrotreating andhydrocracking beds or stages can be the same.

In yet another aspect, a hydroprocessing reaction system ay include morethan one hydrocracking stage. If multiple hydrocracking stages arepresent, at least one hydrocracking stage can have effectivehydrocracking conditions as described above, including a hydrogenpartial pressure of at least about 1500 psig (10.3 MPag). In such anaspect, other hydrocracking processes can be performed under conditionsthat may include lower hydrogen partial pressures. Suitablehydrocracking conditions for an additional hydrocracking stage caninclude, but are not limited to, temperatures of about 500° F. (260° C.)to about 840° F. (449° C.), hydrogen partial pressures of from about 250psig to about 5000 psig (1.8 MPag, to 34.6 MPag), liquid hourly spacevelocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogen treat gas rates offrom 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000 SCF/B). In otherembodiments, the conditions for an additional hydrocracking stage caninclude temperatures in the range of about 600° F. (343° C.) to about815° F. (435° C.), hydrogen partial pressures of from about 500 psig toabout 3000 psig (3.5 MPag-20.9 MPag), and hydrogen treat gas rates offrom about 213 m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000 SCF/B). TheLHSV can be from about 0.25 ⁻¹ to about 50 h⁻¹, or from about 0.5 h⁻¹ toabout 20 h⁻¹, and preferably from about 1.0 h⁻¹ to about 4.0 h⁻¹.

Hydroprocessed Effluent—Solvent Dewaxing to Form Group I Bright Stock

The hydroprocessed deasphalted oil (optionally including hydroprocessedvacuum gas oil) can be separated to form one or more fuel boiling rangefractions (such as naphtha or distillate fuel boiling range fractions)and at least one lubricant base stock boiling range fraction. Thelubricant base stock boiling range fraction(s) can then be solventdewaxed to produce a lubricant base stock product with a reduced (oreliminated) tendency to form haze. Lubricant base stocks (includingbright stock) formed by hydroprocessing a deasphalted oil and thensolvent dewaxing the hydroprocessed effluent can tend to be Group I basestocks due to having an aromatics content of at least 10 wt %.

Solvent dewaxing typically involves mixing a feed with chilled dewaxingsolvent to form an oil-solvent solution. Precipitated wax is thereafterseparated by, for example, filtration. The temperature and solvent areselected so that the oil is dissolved by the chilled solvent while thewax is precipitated.

An example of a suitable solvent dewaxing process involves the use of acooling tower where solvent is prechilled and added incrementally atseveral points along the height of the cooling tower. The oil-solventmixture is agitated during the chilling step to permit substantiallyinstantaneous mixing of the prechilled solvent with the oil. Theprechilled solvent is added incrementally along the length of thecooling tower so as to maintain an average chilling rate at or below 10°F. per minute, usually between about 1 to about 5° F. per minute. Thefinal temperature of the oil-solvent/precipitated wax mixture in thecooling tower will usually be between 0 and 50° F. (−17.8 to 10° C.).The mixture may then be sent to a scraped surface chiller to separateprecipitated wax from the mixture.

Representative dewaxing solvents are aliphatic ketones having 3-6 carbonatoms such as methyl ethyl ketone and methyl isobutyl ketone, lowmolecular weight hydrocarbons such as propane and butane, and mixturesthereof. The solvents may be mixed with other solvents such as benzene,toluene or xylene.

In general, the amount of solvent added will be sufficient to provide aliquid/solid weight ratio between the range of 5/1 and 20/1 at thedewaxing temperature and a solvent/oil volume ratio between 15/1 to 5/1.The solvent dewaxed oil can be dewaxed to a pour point of −6° C. orless, or −10° C. or less, or −15° C. or less, depending on the nature ofthe target lubricant base stock product. Additionally or alternately,the solvent dewaxed oil can be dewaxed to a cloud point of −2° C. orless, or −5° C. or less, or −10° C. or less, depending on the nature ofthe target lubricant base stock product. The resulting solvent dewaxedoil can be suitable for use in forming one or more types of Group I basestocks. Preferably, a bright stock formed from the solvent dewaxed oilcan have a cloud point below −5° C. The resulting solvent dewaxed oilcan have a viscosity index of at least 90, or at least 95, or at least100. Preferably, at least 10 wt % of the resulting solvent dewaxed oil(or at least 20 wt %, or at least 30 wt %) can correspond to a Group Ibright stock having a kinematic viscosity at 100° C. of at least 15 cSt,or at least 20 cSt, or at least 25 cSt, such as up to 50 cSt or more.

In some aspects, the reduced or eliminated tendency to form haze for thelubricant base stocks formed from the solvent dewaxed oil can bedemonstrated by a reduced or minimized difference between the cloudpoint temperature and pour point temperature for the lubricant basestocks. In various aspects, the difference between the cloud point andpour point for the resulting solvent dewaxed oil and/or for one or morelubricant base stocks, including one or more bright stocks, formed fromthe solvent dewaxed oil, can be 22° C. or less, or 20° C. or less, or15° C. or less, or 10° C. or less, or 8° C. or less, or 5° C. or less.Additionally or alternately, a reduced or minimized tendency for abright stock to form haze over time can correspond to a bright stockhaving a cloud point of −10° C. or less, or −8° C. or less, or −5° C. orless, or −2° C. or less.

Additional Hydroprocessing—Catalytic Dewaxing, Hydrofinishing, andOptional Hydrocracking

In some alternative aspects, at least a lubricant boiling range portionof the hydroprocessed deasphalted oil can be exposed to furtherhydroprocessing (including catalytic dewaxing) to form either Group Iand/or Group II base stocks, including Group I and/or Group II brightstock. In some aspects, a first lubricant boiling range portion of thehydroprocessed deasphalted oil can be solvent dewaxed as described abovewhile a second lubricant boiling range portion can be exposed to furtherhydroprocessing. In other aspects, only solvent dewaxing or only furtherhydroprocessing can be used to treat a lubricant boiling range portionof the hydroprocessed deasphalted oil.

Optionally, the further hydroprocessing of the lubricant boiling rangeportion of the hydroprocessed deasphalted oil can also include exposureto hydrocracking conditions before and/or after the exposure to thecatalytic dewaxing conditions. At this point in the process, thehydrocracking can be considered “sweet” hydrocracking, as thehydroprocessed deasphalted oil can have a sulfur content of 200 wppm orless.

Suitable hydrocracking conditions can include exposing the feed to ahydrocracking catalyst as previously described above. Optionally, it canbe preferable to use a USY zeolite with a silica to alumina ratio of atleast 30 and a unit cell size of less than 24.32 Angstroms as thezeolite for the hydrocracking catalyst, in order to improve the VIuplift from hydrocracking and/or to improve the ratio of distillate fuelyield to naphtha fuel yield in the fuels boiling range product.

Suitable hydrocracking conditions can also include temperatures of about500° F. (260° C.) to about 840° F. (449° C.), hydrogen partial pressuresof from about 1500 psig to about 5000 psig (10.3 MPag to 34.6 MPag),liquid hourly space velocities of from 0.05 h⁻¹ to 10 h⁻¹, and hydrogentreat gas rates of from 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to 10,000SCF/B). In other embodiments, the conditions can include temperatures inthe range of about 600° F. (343° C.) to about 815° F. (435° C.),hydrogen partial pressures of from about 1500 psig to about 3000 psig(10.3 MPag-20.9 MPag), and hydrogen treat gas rates of from about 213m³/m³ to about 1068 m³/m³ (1200 SCF/B to 6000 SCF/B). The LHSV can befrom about 0.25 h⁻¹ to about 50 h⁻¹, or from about 0.5 h⁻¹ to about 20h⁻¹ , and preferably from about 1.0 h⁻¹ to about 4.0 h⁻¹.

For catalytic dewaxing, suitable dewaxing catalysts can includemolecular sieves such as crystalline aluminosilicates (zeolites). In anembodiment, the molecular sieve can comprise, consist essentially of, orbe ZSM-22, ZSM-23, ZSM-48. Optionally but preferably, molecular sievesthat are selective for dewaxing by isomerization as opposed to crackingcan be used, such as ZSM-48, ZSM-23, or a combination thereof.Additionally or alternately, the molecular sieve can comprise, consistessentially of, or be a 10-member ring 1-D molecular sieve, such asEU-2, EU-11, ZBM-30, ZSM-48, or ZSM-23. ZSM-48 is most preferred. Notethat a zeolite having the ZSM-23 structure with a silica to aluminaratio of from about 20:1 to about 40:1 can sometimes be referred to asSSZ-32. Optionally but preferably, the dewaxing catalyst can include abinder for the molecular sieve, such as alumina, titania, silica,silica-alumina, zirconia, or a combination thereof, for example aluminaand/or titania or silica and/or zirconia and/or titania.

Preferably, the dewaxing catalysts used in processes according to theinvention are catalysts with a low ratio of silica to alumina. Forexample, for ZSM-48, the ratio of silica to alumina in the zeolite canbe about 100:1 or less, such as about 90:1 or less, or about 75:1 orless, or about 70:1 or less. Additionally or alternately, the ratio ofsilica to alumina in the ZSM-48 can be at least about 50:1, such as atleast about 60:1, or at least about 65:1.

In various embodiments, the catalysts according to the invention furtherinclude a metal hydrogenation component. The metal hydrogenationcomponent is typically a Group VI and/or a Group VIII metal. Preferably,the metal hydrogenation component can be a combination of a non-nobleGroup VIII metal with a Group VI metal. Suitable combinations caninclude Ni, Co, or Fe with Mo or W, preferably Ni with Mo or W.

The metal hydrogenation component may be added to the catalyst in anyconvenient manner. One technique for adding the metal hydrogenationcomponent is by incipient wetness. For example, after combining azeolite and a binder, the combined zeolite and binder can be extrudedinto catalyst particles. These catalyst particles can then be exposed toa solution containing a suitable metal precursor. Alternatively, metalcan be added to the catalyst by ion exchange, where a metal precursor isadded to a mixture of zeolite (or zeolite and binder) prior toextrusion.

The amount of metal in the catalyst can be at least 0.1 wt % based oncatalyst, or at least 0.5 wt %, or at least 1.0 wt %, or at least 2.5 wt%, or at least 5.0 wt %, based on catalyst. The amount of metal in thecatalyst can be 20 wt % or less based on catalyst, or 10 wt % or less,or 5 wt % or less, or 2.5 wt % or less, or 1 wt % or less. Forembodiments where the metal is a combination of a non-noble Group VIIImetal with a Group VI metal, the combined amount of metal can be from0.5 wt % to 20 wt %, or 1 wt % to 15 wt %, or 2.5 wt % to 10 wt %.

The dewaxing catalysts useful in processes according to the inventioncan also include a binder. In some embodiments, the dewaxing catalystsused in process according to the invention are formulated using a lowsurface area binder, a low surface area binder represents a binder witha surface area of 100 m²/g or less, or 80 m²/g or less, or 70 m²/g orless. Additionally or alternately, the binder can have a surface area ofat least about 25 m²/g. The amount of zeolite in a catalyst formulatedusing a binder can be from about 30 wt % zeolite to 90 wt % zeoliterelative to the combined weight of binder and zeolite. Preferably, theamount of zeolite is at least about 50 wt % of the combined weight ofzeolite and binder, such as at least about 60 wt % or from about 65 wt %to about 80 wt %.

Without being bound by any particular theory, it is believed that use ofa low surface area binder reduces the amount of binder surface areaavailable for the hydrogenation metals supported on the catalyst. Thisleads to an increase in the amount of hydrogenation metals that aresupported within the pores of the molecular sieve in the catalyst.

A zeolite can be combined with binder in any convenient manner. Forexample, a bound catalyst can be produced by starting with powders ofboth the zeolite and binder, combining and mulling the powders withadded water to form a mixture, and then extruding the mixture to producea bound catalyst of a desired size. Extrusion aids can also be used tomodify the extrusion flow properties of the zeolite and binder mixture.The amount of framework alumina in the catalyst may range from 0.1 to3.33 wt %, or 0.1 to 2.7 wt %, or 0.2 to 2 wt %, or 0.3 to 1 wt %.

Effective conditions for catalytic dewaxing of a feedstock in thepresence of a dewaxing catalyst can include a temperature of from 280°C. to 450° C., preferably 343° C. to 435° C., a hydrogen partialpressure of from 3.5 MPag to 34.6 MPag (500 psig to 5000 psig),preferably 4.8 MPag to 20.8 MPag, and a hydrogen circulation rate offrom 178 m³/m³ (1000 SCF/B) to 1781 m³/m³ (10,000 scf/B), preferably 213m³/m³ (1200 SCF/B) to 1068 m³/m³ (6000 SCF/B). The LHSV can be fromabout 0.2 h⁻¹ to about 10 h⁻¹, such as from about 0.5 h⁻¹ to about 5 h⁻¹and/or from about 1 h⁻¹ to about 4 h⁻¹.

Before and/or after catalytic dewaxing, the hydroprocessed deasphaltedoil (i.e., at least a lubricant boiling range portion thereof) canoptionally be exposed to an aromatic saturation catalyst, which canalternatively be referred to as a hydrofinishing catalyst. Exposure tothe aromatic saturation catalyst can occur either before or afterfractionation. If aromatic saturation occurs after fractionation, thearomatic saturation can be performed on one or more portions of thefractionated product. Alternatively, the entire effluent from the lasthydrocracking or dewaxing process can be hydrofinished and/or undergoaromatic saturation.

Hydrofinishing and/or aromatic saturation catalysts can includecatalysts containing Group VI metals, Group VIII metals, and mixturesthereof. In an embodiment, preferred metals include at least one metalsulfide having a strong hydrogenation function. In another embodiment,the hydrofinishing catalyst can include a Group VIII noble metal, suchas Pt, Pd, or a combination thereof. The mixture of metals may also bepresent as bulk metal catalysts wherein the amount of metal is about 30wt. % or greater based on catalyst. For supported hydrotreatingcatalysts, suitable metal oxide supports include low acidic oxides suchas silica, alumina, silica-aluminas or titanic, preferably alumina. Thepreferred hydrofinishing catalysts for aromatic saturation will compriseat least one metal having relatively strong hydrogenation function on aporous support. Typical support materials include amorphous orcrystalline oxide materials such as alumina, silica, and silica-alumina.The support materials may also be modified, such as by halogenation, orin particular fluorination. The metal content of the catalyst is oftenas high as about 20 weight percent for non-noble metals. In anembodiment, a preferred hydrofinishing catalyst can include acrystalline material belonging to the M41S class or family of catalysts.The M41S family of catalysts are mesoporous materials having high silicacontent. Examples include MCM-41, MCM-48 and MCM-50. A preferred memberof this class is MCM-41

Hydrofinishing conditions can include temperatures from about 125° C. toabout 425° C., preferably about 180° C. to about 280° C., a hydrogenpartial pressure from about 500 psig (3.4 MPa) to about 3000 psig (20.7MPa), preferably about 1500 psig (10.3 MPa) to about 2500 psig (17.2MPa), and liquid hourly space velocity from about 0.1 hr⁻¹ to about 5hr⁻¹ LHSV, preferably about 0.5 hr⁻¹ to about 1.5 hr ⁻¹. Additionally, ahydrogen treat gas rate of from 35.6 m³/m³ to 1781 m³/m³ (200 SCF/B to10,000 SCF/B) can be used.

Solvent Processing of Catalytically Dewaxed Effluent or Input Flow toCatalytic Dewaxing

For deasphalted oils derived from propane deasphalting, the furtherhydroprocessing (including catalytic dewaxing) can be sufficient to formlubricant base stocks with low haze formation and unexpectedcompositional properties. For deasphalted oils derived from C₄₊deasphalting, after the further hydroprocessing (including catalyticdewaxing), the resulting catalytically dewaxed effluent can be solventprocessed to form one or more lubricant base stock products with areduced or eliminated tendency to form haze. The type of solventprocessing can be dependent on the nature of the initial hydroprocessing(hydrotreatment and/or hydrocracking) and the nature of the furtherhydroprocessing (including dewaxing).

In aspects where the initial hydroprocessing is less severe,corresponding to 10 wt % to 40 wt % conversion relative to ˜700° F.(370° C.), the subsequent solvent processing can correspond to solventdewaxing. The solvent dewaxing can be performed in a manner similar tothe solvent dewaxing described above. However, this solvent dewaxing canbe used to produce a Group II lubricant base stock. In some aspects,when the initial hydroprocessing corresponds to 10 wt % to 40 wt %conversion relative to 370° C., the catalytic dewaxing during furtherhydroprocessing can also be performed at lower severity, so that atleast 6 wt % wax remains in the catalytically dewaxed effluent, or atleast 8 wt %, or at least 10 wt %, or at least 12 wt %, or at least 15wt %, such as up to 20 wt %. The solvent dewaxing can then be used toreduce the wax content in the catalytically dewaxed effluent by 2 wt %to 10 wt %. This can produce a solvent dewaxed oil product having a waxcontent of 0.1 wt % to 12 wt %, or 0.1 wt % to 10 wt %, or 0.1 wt % to 8wt %, or 0.1 wt % to 6 wt %, or 1 wt % to 12 wt %, or 1 wt % to 10 wt %,or 1 wt % to 8 wt %, or 4 wt % to 12 wt %, or 4 wt % to 10 wt %, or 4 wt% to 8 wt %, or 6 wt % to 12 wt %, or 6 wt % to 10 wt %. In particular,the solvent dewaxed oil can have a wax content of 0.1 wt % to 12 wt %,or 0.1 wt % to 6 wt %, or 1 wt % to 10 wt %, or 4 wt % to 12 wt %.

In other aspects, the subsequent solvent processing can correspond tosolvent extraction. Solvent extraction can be used to reduce thearomatics content and/or the amount of polar molecules. The solventextraction process selectively dissolves aromatic components to form anaromatics-rich extract phase while leaving the more paraffiniccomponents in an aromatics-poor raffinate phase. Naphthenes aredistributed between the extract and raffinate phases. Typical solventsfor solvent extraction include phenol, furfural and N-methylpyrrolidone. By controlling the solvent to oil ratio, extractiontemperature and method of contacting distillate to be extracted withsolvent, one can control the degree of separation between the extractand raffinate phases. Any convenient type of liquid-liquid extractor canbe used, such as a counter-current liquid-liquid extractor. Depending onthe initial concentration of aromatics in the deasphalted oil, theraffinate phase can have an aromatics content of 5 wt % to 25 wt %. Fortypical feeds, the aromatics contents can be at least 10 wt %.

Optionally, the raffinate from the solvent extraction can beunder-extracted. In such aspects, the extraction is carried out underconditions such that the raffinate yield is maximized while stillremoving most of the lowest quality molecules from the feed. Raffinateyield may be maximized by controlling extraction conditions, forexample, by lowering the solvent to oil treat ratio and/or decreasingthe extraction temperature. In various aspects, the raffinate yield fromsolvent extraction can be at least 40 wt %, or at least 50 wt %, or atleast 60 wt %, or at least 70 wt %.

The solvent processed oil (solvent dewaxed or solvent extracted) canhave a pour point of −6° C. or les, or −10° C. or less, or −15° C. orless, or −20° C. or less, depending on the nature of the targetlubricant base stock product. Additionally or alternately, the solventprocessed oil (solvent dewaxed or solvent extracted) can have a cloudpoint of −2° C. or less, or −5° C. or less, or −10° C. or less,depending on the nature of the target lubricant base stock product. Pourpoints and cloud points can be determined according to ASTM D97 and ASTMD2500, respectively. The resulting solvent processed oil can be suitablefor use in forming one or more types of Group II base stocks. Theresulting solvent dewaxed oil can have a viscosity index of at least 80,or at least 90, or at least 95, or at least 100, or at least 110, or atleast 120. Viscosity index can be determined according to ASTM D2270.Preferably, at least 10 wt % of the resulting solvent processed oil (orat least 20 wt %, or at least 30 wt %) can correspond to a Group IIbright stock having a kinematic viscosity at 100° C. of at least 14 cSt,or at least 15 cSt, or at least 20 cSt, or at least 25 cSt, or at least30 cSt, or at least 32 cSt, such as up to 50 cSt or more. Additionallyor alternately, the Group II bright stock can have a kinematic viscosityat 40° C. of at least 300 cSt, or at least 320 cSt, or at least 340 cSt,or at least 350 cSt, such as up to 500 cSt or more. Kinematic viscositycan be determined according to ASTM D445. Additionally or alternately,the Conradson Carbon residue content can be about 0.1 wt % or less, orabout 0.02 wt % or less. Conradson Carbon residue content can bedetermined according to ASTM D4530. Additionally or alternately, theresulting base stock can have a turbidity of at least 1.5 (incombination with a cloud point of less than 0° C.), or can have aturbidity of at least 2.0, and/or can have a turbidity of 4.0 or less,or 3.5 or less, or 3.0 or less. In particular, the turbidity can be 1.5to 4.0, or 1.5 to 3.0, or 2.0 to 4.0, or 2.0 to 3.5.

The reduced or eliminated tendency to form haze for the lubricant basestocks formed from the solvent processed oil can be demonstrated by thereduced or minimized difference between the cloud point temperature andpour point temperature for the lubricant base stocks. In variousaspects, the difference between the cloud point and pour point for theresulting solvent dewaxed oil and/or for one or more Group II lubricantbase stocks, including one or more bright stocks, formed from thesolvent processed oil, can be 22° C. or less, or 20° C. or less, or 15°C. or less, or 10° C. or less, such as down to about 1° C. ofdifference.

In some alternative aspects, the above solvent processing can beperformed prior to catalytic dewaxing.

Group II Base Stock Products

For deasphalted oils derived from propane, butane, pentane, hexane andhigher or mixtures thereof, the further hydroprocessing (includingcatalytic dewaxing) and potentially solvent processing can be sufficientto form lubricant base stocks with low haze formation (or no hazeformation) and novel compositional properties. Traditional productsmanufactured today with kinematic viscosity of about 32 cSt at 100° C.contain aromatics that are >10% and/or sulfur that is >0.03% of the baseoil.

In various aspects, base stocks produced according to methods describedherein can have a kinematic viscosity of at least 14 cSt, or at least 20cSt, or at least 25 cSt, or at least 30 cSt, or at least 32 cSt at 100°C. and can contain less than 10 wt % aromatics/greater than 90 wt %saturates and less than 0.03% sulfur. Optionally, the saturates contentcan be still higher, such as greater than 95 wt %, or greater than 97 wt%. In addition, detailed characterization of the branchiness (branching)of the molecules by C-NMR reveals a high degree of branch points asdescribed fluffier below in the examples. This can be quantified byexamining the absolute number of methyl branches, or ethyl branches, orpropyl branches individually or as combinations thereof. This can alsobe quantified by looking at the ratio of branch points (methyl, ethyl,or propyl) compared to the number of internal carbons, labeled asepsilon carbons by C-NMR. This quantification of branching can be usedto determine whether a base stock will be stable against haze formationover time. For ¹³C-NMR results reported herein, samples were prepared tobe 25-30 wt % in CDCl₃ with 7% Chromium (III)-acetylacetonate added as arelaxation agent. ¹³C NMR experiments were performed on a JEOL ECS NMRspectrometer for which the proton resonance frequency is 400 MHz.Quantitative ¹³C NMR experiments were performed at 27° C. using aninverse gated decoupling experiment with a 45° flip angle, 6.6 secondsbetween pulses, 64 K data points and 2400 scans. All spectra werereferenced to TMS at 0 ppm. Spectra were processed with 0.2-1 Hz of linebroadening and baseline correction was applied prior to manualintegration. The entire spectrum was integrated to determine the mole %of the different integrated areas as follows: 170-190 PPM (aromatic C);30-29.5 PPM (epsilon carbons); 15-14.5 PPM (terminal and pendant propylgroups) 14.5-14 PPM-Methyl at the end of a long chain (alpha); 12-10 PPM(pendant and terminal ethyl groups). Total methyl content was obtainedfrom proton NMR. The methyl signal at 0-1.1 PPM was integrated. Theentire spectrum was integrated to determine the mole % of methyls.Average carbon numbers obtained from gas chromatography were used toconvert mole % methyls to total methyls.

Also unexpected in the composition is the discovery using FourierTransform Ion Cyclotron Resonance-Mass Spectrometry (FTICR-MS) and/orField Desorption Mass Spectrometry (FDMS) that the prevalence of smallernaphthenic ring structures below 6 or below 7 or below 8 naphthene ringscan be similar but the residual numbers of larger naphthenic ringsstructures with 7 or more rings or 8+ rings or 9+ rings or 10+ rings isdiminished in base stocks that are stable against haze formation.

For FTICR-MS results reported herein, the results were generatedaccording to the method described in U.S. Pat. No. 9,418,828. The methoddescribed in U.S. Pat. No. 9,418,828 generally involves using laserdesorption with Ag ion complexation (LDI-Ag) to ionize petroleumsaturates molecules (including 538° C.+ molecules) without fragmentationof the molecular ion structure. Ultra-high resolution Fourier TransformIon Cyclotron Resonance Mass Spectrometry is applied to determine exactelemental formula of the saturates-Ag cations and correspondingabundances. The saturates fraction composition can be arranged byhomologous series and molecular weights. The portion of U.S. Pat. No.9,418,828 related to determining the content of saturate ring structuresin a sample is incorporated herein by reference.

For FDMS results reported herein, Field desorption (FD) is a softionization method in which a high-potential electric field is applied toan emitter (a filament from which tiny “whiskers” have formed) that hasbeen coated with a diluted sample resulting in the ionization of gaseousmolecules of the analyte. Mass spectra produced by FD are dominated bymolecular radical cations M⁺or in some cases protonated molecular ions[M+H]⁺. Because FDMS cannot distinguish between molecules with ‘n’naphthene rings and molecules with ‘n+7’ rings, the FDMS data was“corrected” by using the FTICR-MS data from the most similar sample. TheFDMS correction was performed by applying the resolved ratio of “n” to“n+7” rings from the FTICR-MS to the unresolved FDMS data for thatparticular class of molecules. Hence, the FDMS data is shown as“corrected” in the figures.

Base oils of the compositions described above have further been found toprovide the advantage of being haze free upon initial production andremaining haze free for extended periods of time. This is an advantageover the prior art of high saturates heavy base stocks that wasunexpected.

Additionally, it has been found that these base stocks can be blendedwith additives to form formulated lubricants, such as but not limited tomarine oils, engine oils, greases, paper machine oils, and gear oils.These additives may include, but are not restricted to, detergents,dispersants, antioxidants, viscosity modifiers, and pour pointdepressants. More generally, a formulated lubricating including a basestock produced from a deasphalted oil may additionally contain one ormore of the other commonly used lubricating oil performance additivesincluding but not limited to antiwear agents, dispersants, otherdetergents, corrosion inhibitors, rust inhibitors, metal deactivators,extreme pressure additives, anti-seizure agents, wax modifiers,viscosity index improvers, viscosity modifiers, fluid-loss additives,seal compatibility agents, friction modifiers, lubricity agents,anti-staining agents, chromophoric agents, defoamants, demulsifiers,emulsifiers, densifiers, wetting agents, gelling agents, tackinessagents, colorants, and others. For a review of many commonly usedadditives, see Klamann in Lubricants and Related Products, VerlagChemie, Deerfield Beach, Fla.; ISBN 0-89573-177-0. These additives arecommonly delivered with varying amounts of diluent oil, that may rangefrom 5 weight percent to 50 weight percent.

When so blended, the performance as measured by standard low temperaturetests such as the Mini-Rotary Viscometer (MRV) and Brookfield test hasbeen shown to be superior to formulations blended with traditional baseoils.

It has also been found that the oxidation performance, when blended intoindustrial oils using common additives such as, but not restricted to,defoamants, pour point depressants, antioxidants, rust inhibitors, hasexemplified superior oxidation performance in standard oxidation testssuch as the US Steel Oxidation test compared to traditional base stocks.

Other performance parameters such as interfacial properties, depositcontrol, storage stability, and toxicity have also been examined and aresimilar to or better than traditional base oils.

In addition to being blended with additives, the base stocks describedherein can also be blended with other base stocks to make a base oil.These other base stocks include solvent processed base stocks,hydroprocessed base stocks, synthetic base stocks, base stocks derivedfrom Fisher-Tropsch processes, PAO, and naphthenic base stocks.Additionally or alternately, the other base stocks can include Group Ibase stocks, Group II base stocks, Group III base stocks, Group IV basestocks, and/or Group V base stocks. Additionally or alternately, stillother types of base stocks for blending can include hydrocarbylaromatics, alkylated aromatics, esters (including synthetic and/orrenewable esters), and or other non-conventional or unconventional basestocks. These base oil blends of the inventive base stock and other basestocks can also be combined with additives, such as those mentionedabove, to make formulated lubricants.

CONFIGURATION EXAMPLES

FIG. 1 schematically shows a first configuration for processing of adeasphalted oil feed 110. Optionally, deasphalted oil feed 110 caninclude a vacuum gas oil boiling range portion. In FIG. 1, a deasphaltedoil feed 110 is exposed to hydrotreating and/or hydrocracking catalystin a first hydroprocessing stage 120. The hydroprocessed effluent fromfirst hydroprocessing stage 120 can be separated into one or more fuelsfractions 127 and a 370° C.+ fraction 125. The 370° C.+ fraction 125 canbe solvent dewaxed 130 to form one or more lubricant base stockproducts, such as one or more light neutral or heavy neutral base stockproducts 132 and a bright stock product 134.

FIG. 2 schematically shows a second configuration for processing adeasphalted oil feed 110. In FIG. 2, solvent dewaxing stage 130 isoptional. The effluent from first hydroprocessing stage 120 can beseparated to form at least one or more fuels fractions 127, a first 370°C. portion 245, and a second optional 370° C.+ portion 225 that can beused as the input for optional solvent dewaxing stage 130. The first370° C.+ portion 245 can be used as an input for a secondhydroprocessing stage 250. The second hydroprocessing stage cancorrespond to a sweet hydroprocessing stage for performing catalyticdewaxing, aromatic saturation, and optionally further performinghydrocracking. In FIG. 2, at least a portion 253 of the catalyticallydewaxed output 255 from second hydroprocessing stage 250 can be solventdewaxed 260 to form at least a solvent processed lubricant boiling rangeproduct 265 that has a T10 boiling point of at least 510° C. and thatcorresponds to a Group II bright stock.

FIG. 3 schematically shows another configuration for producing a GroupII bright stock. In FIG. 3, at least a portion 353 of the catalyticallydewaxed output 355 from the second hydroprocessing stage 250 is solventextracted 370 to form at least a processed lubricant boiling rangeproduct 375 that has a T10 boiling point of at least 510° C. and thatcorresponds to a Group II bright stock.

FIG. 6 schematically shows yet another configuration for producing aGroup II bright stock. In FIG. 6, a vacuum resid feed 675 and adeasphalting solvent 676 is passed into a deasphalting unit 680. In someaspects, deasphalting unit 680 can perform propane deasphalting, but inother aspects a C₄₊ solvent can be used. Deasphalting unit 680 canproduce a rock or asphalt fraction 682 and a deasphalted oil 610.Optionally, deasphalted oil 610 can be combined with another vacuum gasoil boiling range feed 671 prior to being introduced into first (sour)hydroprocessing stage 620. A lower boiling portion 627 of the effluentfrom hydroprocessing stage 620 can be separated out for further useand/or processing as one or more naphtha fractions and/or distillatefractions. A higher boiling portion 625 of the hydroprocessing effluentcan be a) passed into a second (sweet) hydroprocessing stage 650 and/orb) withdrawn 626 from the processing system for use as a fuel, such as afuel oil or fuel oil blendstock. Second hydroprocessing stage 650 canproduce an effluent that can be separated to form one or more fuelsfractions 657 and one or more lubricant base stock fractions 655, suchas one or more bright stock fractions.

In some aspects, a configuration similar to FIG. 6 can be used togenerate a wide boiling range Group II heavy neutral base stock. Forexample, a high viscosity vacuum resid feed can be processed by propanedeasphalting to form deasphalted oil and rock. The deasphalted oil canthen be processed under conditions similar to those that could be usedfor an initial stage of hydroprocessing for lubricant base oilproduction. This can include, for example, exposing the deasphalted oilsequentially to a hydrotreating catalyst, a hydrocracking catalyst, andan aromatic saturation catalyst. A stacked bed catalyst arrangement canbe suitable for exposing the deasphalted oil to the catalysts. Thecatalyst can be any convenient type ofhydrotreating/hydrocracking/aromatic saturation catalysts that aresuitable for use in a sour processing environment (such as anenvironment where the initial feed had a sulfur content of more than 500wppm). Examples of suitable catalyst can include, but are not limitedto, bulk and/or supported catalysts containing Group VIII and Group VImetals, such as commercially available NiMo, NiMoW, or CoMo basedcatalysts. The hydroprocessing conditions for exposure to the catalystscan be selected to produce a hydroprocessed effluent having a sulfurcontent of 20 wppm or less and/or a nitrogen content of 5 wppm or less.

In addition to reducing the sulfur and/or nitrogen content, anotherrequirement of the first stage hydroprocessing can be to reduce theviscosity of the first stage hydroprocessed effluent to a desired level.Deasphalted oil from propane deasphalting can typically have a kinematicviscosity at 100° C. of 30 cSt to 80 cSt. In various aspects, thehydroprocessing severity in the first hydroprocessing stage can besufficient so that the 370° C.+ portion of the first hydroprocessingstage effluent can have a kinematic viscosity at 100° C. of 8.0 cSt to20 cSt, or 8 cSt to 16 cSt. To achieve this, the severity of thereactions in the first hydroprocessing stage can be selected so that thenet conversion across the first hydroprocessing stage relative to 370°C. is between 15 wt % to 40 wt %, or 7 wt % to 25 wt %. It is noted thatsubstantially all of a typical propane deasphalted oil will have aboiling point greater than 370° C., so a conversion (for example) of 15wt % to 40 wt % relative to 370° C. for a propane deasphalted oil cancorrespond to conversion of 15 wt % to 40 wt % of the total feedrelative to 370′C.

Based on the first stage hydroprocessing, a first stage hydroprocessedeffluent can be produced that has less than 50 wppm S (or less than 20wppm, or less than 10 wppm), less than 20 wppm N (or less than 10 wppm,or less than 5 wppm), and 60 wt % or more (relative to a weight of thetotal effluent) of a 370° C.+ fraction with a kinematic viscosity 100°C. of 8 cSt to 20 cSt, or 8 cSt to 16 cSt. The first stagehydroprocessed effluent can undergo separation prior to furtherprocessing in a second stage. For example, the 370° C.− portion (lightends and fuels boiling range portions) of the first stage hydroprocessedeffluent can be separated from the 370° C.+ portion of the effluent.Because the first stage hydroprocessed effluent is being separated intolower boiling cuts and a remaining 370° C.+ fraction, the separation canoptionally be performed by atmospheric distillation and/or by aseparation technique comprising separating at a pressure of at least 90kPa-a, or at least 100 kPa-a. It is noted that this separation may notbe ideal, so that the T5 boiling point for the “370° C.+” portion, afterseparation, may actually be lower than 370° C. In this description andthe claims below, it is noted that the “370° C.+” portion of theeffluent, after separation, may include as much as 10 wt % of componentsthat boil below 370° C. Additionally, it is noted that the “370° C.+”portion also can include a substantial portion of components that boilabove the lubricant boiling range, such as components having a boilingpoint above 566° C.

The 370° C.+ portion of the effluent (possibly including some componentsboiling below 370° C.) can then be exposed to a second catalyticprocessing stage. The second catalytic processing stage can includecatalytic dewaxing and hydrofinishing catalysts that include Group VIIInoble metals, such as Pt, Pd, or a combination thereof. The conversionacross the second catalytic processing stage can be 1 wt % to 10 wt %relative to 370° C., or 10 wt % to 20 wt %, depending on the amount ofconversion in the first hydroprocessing stage. As a result, the overallyield of heavy neutral lubricant basestock relative to the initialpropane deasphalted oil can be 50 wt % to 89 wt %, or 54 wt % to 85 wt%, or 60 wt % to 90 wt %. Optionally but preferably, the catalyticdewaxing can be performed using 1-D 10-member ring zeolitic dewaxingcatalyst, such as ZSM-48 or ZSM-23. These types of catalysts can allowfor production of a second hydroprocessing stage effluent where the 370°C.+ portion of the effluent has a relatively flat profile of pour pointrelative to boiling point. This can allow higher boiling 566° C.+components to remain in a heavy neutral lubricant base stock productwhile still satisfying other desired lubricant base stock properties.The additional 566° C.+ components can be fluxed in the base stock bythe 427° C.− portion of the base stock. For example, the 370° C.+portion of the second hydroprocessing stage effluent (corresponding tothe potential heavy neutral base stock) can have a T5 distillation pointof at least 350° C. The 370° C+ portion can also have a T25 distillationpoint or T30 distillation point of 427° C. or less. The 370° C.+ portioncan further have a T95 distillation point or 190 distillation point ofat least 566° C.

After the second stage hydroprocessing, a second separation can beperformed to separate the 370° C.+ portion of the effluent from the 370°C.− portion. Optionally, the second separation can be performed byatmospheric distillation and/or by a separation technique comprisingseparating at a pressure of at least 90 kPa-a, or at least 100 kPa-a.The 370° C.+ portion can then be suitable, for example, for use as aheavy neutral basestock. In addition to having a sulfur content of 50wppm or less (or 20 wppm or less, or 10 wppm or less) and a nitrogencontent of 20 wppm or less (or 10 wppm or less, or 5 wppm or less), the370° C.+ portion of the second hydroprocessed effluent can have anaromatics content of 10 wt % or less, a VI of at least 100 (or at least105, or at least 110, or at least 120), and a kinematic viscosity at100° C. of 8 cSt to 20 cSt, or 8 cSt to 18 cSt, or 8 cSt to 16 cSt.

Optionally, a noble metal hydrocracking catalyst could be included priorto dewaxing. In this type of optional aspect, a portion of theconversion can be shifted from the first hydroprocessing stage (sourconditions) to the second hydroprocessing stage (sweet conditions). Inthis type of optional aspect, the yield of heavy neutral basestock on C₃deasphalted oil can still be at least 54 wt %. However, the distributionof conversion amounts between the stages can change, so that the amountof conversion relative to 370° C. In the first hydroprocessing stage canbe lower than 15 wt % and/or the conversion in the secondhydroprocessing stage can be greater than 10 wt %.

Example 1

In this example, a deasphalted oil was processed in a configurationsimilar to FIG. 1. The deasphalted oil was derived from deasphalting ofa resid fraction using pentane as a solvent. The properties of thedeasphalted oil are shown in Table 1. The yield of deasphalted oil was75 wt % relative to the feed.

TABLE 1 Deasphalted Oil from Pentane Deasphalting (75 wt % yield) APIGravity 12.2 Sulfur (wt %) 3.72 Nitrogen (wppm) 2557 Ni (wppm) 7.1 V(wppm) 19.7 CCR (wt %) 12.3 Wax (wt %) 4.6 GCD Distillation (wt %) (°C.)  5% 522 10% 543 30% 586 50% 619 70% 660 90% 719

The deasphalted oil in Table 1 was processed at 0.2 hr⁻¹ LHSV, a treatgas rate of 8000 scf/b, and a pressure of 2250 psig over a catalyst fillof 50 vol % demetalization catalyst, 42.5 vol % hydrotreating catalyst,and 7.5% hydrocracking catalyst by volume. The demetallization catalystwas a commercially available large pore supported demetallizationcatalyst. The hydrotreating catalyst was a stacked bed of commerciallyavailable supported NiMo hydrotreating catalyst and commerciallyavailable bulk NiMo catalyst. The hydrocracking catalyst was a standarddistillate selective catalyst used in industry. Such catalysts typicallyinclude NiMo or NiW on a zeolite/alumina support. Such catalyststypically have less than 40 wt % zeolite of a zeolite with a unit cellsize of less than 34.38 Angstroms. A preferred zeolite content can beless than 25 wt % and/or a preferred unit cell size can be less than24.32 Angstroms. Activity for such catalysts can be related to the unitcell size of the zeolite, so the activity of the catalyst can beadjusted by selecting the amount of zeolite. The feed was exposed to thedemetallization catalyst at 745° F. (396° C.) and exposed to thecombination of the hydrotreating and hydrocracking catalyst at 765° F.(407° C.) In an isothermal fashion.

The hydroprocessed effluent was distilled to form a 510° C.+ fractionand a 510° C.− fraction. The 51.0° C.− fraction could be solvent dewaxedto produce lower viscosity (light neutral and/or heavy neutral)lubricant base stocks. The 510° C.+ fraction was solvent dewaxed toremove the wax. The properties of the resulting Group I bright stock areshown in Table 2. The low cloud point demonstrates the haze freepotential of the bright stock, as the cloud point differs from the pourpoint by less than 5° C.

TABLE 2 Group I bright stock properties Product Fraction 510° C.+ VI98.9 KV @100° C. 27.6 KV @40° C. 378 Pour Pt (° C.) −15 Cloud Pt (° C.)−11

Example 2

In this example, a deasphalted oil was processed in a configurationsimilar to FIG. 1. The deasphalted oil described in Table 1 of Example 1was mixed with a lighter boiling range vacuum gas oil in a ratio of 65wt % deasphalted oil to 35 wt % vacuum gas oil. The properties of themixed feed are shown in Table 3.

TABLE 3 Pentane deasphalted oil (65%) and vacuum gas oil (35%)properties API Gravity 13.7 Sulfur (wt %) 3.6 Nitrogen (wppm) 2099 Ni(wppm) 5.2 V (wppm) 14.0 CCR (wt %) 8.1 Wax (wt %) 4.2 GCD Distillation(wt %) (° C.)  5% 422 10% 465 30% 541 50% 584 70% n/a 90% 652

The mixed feed was treated with conditions and catalysts similar tothose used in Example 1, with the exception of an increase in reactortemperature to adjust for catalyst aging and slightly higher conversionamounts. The feed was exposed to the demetallization catalyst at 750° F.(399° C.) and the hydrotreating/hydrocracking catalysts at 770° F. (410°C.). After separation to remove fuels fractions, the 370° C.+ portionwas solvent dewaxed. Bright stocks were formed from the solvent dewaxedeffluent using a 510° C.+ cut and using a second deep cut at 571° C.+.The properties of the two types of possible bright stocks are shown inTable 4. (For clarity, the 510° C.+ bright stock includes the 571° C.+portion. A separate sample was used to form the 571° C.+ bright stockshown in Table 4.)

TABLE 4 Group I bright stocks Product Fraction 510° C.+ 571° C.+ VI108.9 112.2 KV @100° C. 19.9 35.4 KV @40° C. 203 476 Pour Pt (° C.) −14Cloud Pt (° C.) −12

Example 3

A configuration similar to FIG. 1 was used to process a deasphalted oilformed from butane deasphalting (55 wt % deasphalted oil yield). Theproperties of the deasphalted oil are shown in Table 5.

TABLE 5 Butane deasphalted oil (55 wt % yield) API Gravity 14.0 Sulfur(wt %) 2.8 Nitrogen (wppm) 2653 Ni (wppm) 9.5 V (wppm) 14.0 CCR (wt %)8.3 Wax (wt %) 3.9 GCD Distillation (wt %) (° C.)  5% 480 10% 505 30%558 50% 597 70% 641 90% 712

The deasphalted oil was converted to bright stock with low hazecharacteristics using process conditions and catalysts similar to thosein Example 1, with the exception of the reaction temperatures. Thedeasphalted oil was exposed to the first hydroprocessing stage in twoseparate runs with all catalysts (demetallization, hydrotreating,hydrocracking) at a temperature of 371° C. The lower conversion in thesecond run is believed to be due to deactivation of catalyst, as wouldtypically be expected for this type of heavy feed. The effluents fromboth runs were distilled to form a 510° C.+ fraction. The 510° C.+fraction was solvent dewaxed. The resulting solvent dewaxed oils had theproperties shown in Table 6. Table 6 also shows the difference in 370°C. conversion during the two separate runs.

TABLE 6 Group I bright stock properties Product Fraction First runSecond run VI 97.5 90 KV @100° C. 27.3 35.2 KV @40° C. 378 619 Pour Pt(° C.) −19 −18.5 Cloud Pt (° C.) −13 −15 Conversion (wt % relative 54.341.3 to 510° C.)

The low cloud point of both samples demonstrates the haze free potentialof the bright stock, as the cloud point differs from the pour point forboth samples by 6° C. or less.

Example 4

A configuration similar to FIG. 2 was used to process a deasphalted oilformed from butane deasphalting (55 wt % deasphalted oil yield). Theproperties of the deasphalted oil are shown in Table 5. The deasphaltedoil was then hydroprocessed according to the conditions in Example 3. Atleast a portion of the hydroprocessed deasphalted oil was then exposedto further hydroprocessing without being solvent dewaxed.

The non-dewaxed hydrotreated product was processed over combinations oflow unit cell size USY and ZSM-48. The resulting product had a high pourcloud spread differential resulting in a hazy product. However, apost-treat solvent dewaxing was able to remove that haze at a modest 3%loss in yield. Processing conditions for the second hydroprocessingstage included a hydrogen pressure of 1950 psig and a treat gas rate of4000 scf/b. The feed into the second hydroprocessing stage was exposedto a) a 0.6 wt % Pt on USY hydrocracking catalyst (unit cell size lessthan 24.32, silica to alumina ratio of 35, 65 wt % zeolite/35 wt %binder) at 3.1 hr ⁻¹ LHSV and a temperature of 665° F.; b) a 0.6 wt % Pton ZSM-48 dewaxing catalyst (90:1 silica to alumina, 65 wt % zeolite/35wt % binder) at 2.1 hr⁻¹ LHSV and a temperature of 635° F.; and c) 0.3wt % Pt/0.9 wt % Pd on MCM-41 aromatic saturation catalyst (65 wt %zeolite/35 wt % binder) at 0.9 hr⁻¹ LHSV and a temperature of 480° F.The resulting properties of the 510° C.+ portion of the catalyticallydewaxed effluent are shown in Table 7, along with the 510° C. conversionwithin the hydrocracking/catalytic dewaxing/aromatic saturationprocesses

TABLE 7 Catalytically dewaxed effluent Product Fraction VI 104.4 KV@100° C. 26.6 KV @40° C. 337 Pour Pt (° C.) −28 Cloud Pt (° C.) 8.4Conversion (wt % relative 49 to 510° C.)

The product shown in Table 7 was hazy. However, an additional step ofsolvent dewaxing with a loss of only 2.5 wt % yield resulted in a brightand clear product with the properties shown in Table 8. It is noted thatthe pour point and the cloud point differ by slightly less than 20° C.The solvent dewaxing conditions included a slurry temperature of −30°C., a solvent corresponding to 35 wt % methyl ethyl ketone and 65 wt %toluene, and a solvent dilution ratio of 3:1.

TABLE 8 Solvent Processed 510° C.+ product (Group II bright stock)Product Fraction VI 104.4 KV @100° C. 25.7 KV @40° C. 321 Pour Pt (° C.)−27 Cloud Pt (° C.) −7.1

Example 5

The deasphalted oil and vacuum gas oil mixture shown in Table 3 ofExample 2 was processed in a configuration similar to FIG. 3. Theconditions and catalysts in the first hydroprocessing stage were similarto Example 1, with the exception of adjustments in temperature toaccount for catalyst aging. The demetallization catalyst was operated at744° F. (396° C.) and the HDT/HDC combination was operated at 761° F.(405° C.). This resulted in conversion relative to 510° C. of 73.9 wt %and conversion relative to 370° C. of 50 wt %. The hydroprocessdeffluent was separated to remove fuels boiling range portions from a370° C.+ portion. The resulting 370° C.+ portion was then furtherhydroprocessed. The further hydroprocessing included exposing the 370°C.+ portion to a 0.6 wt % Pt on ZSM-48 dewaxing catalyst (70:1 silica toalumina ratio, 65 wt % zeolite to 35 wt % binder) followed by a 0.3 wt %Pt/0.9 wt % Pd on MCM-41 aromatic saturation catalyst (65% zeolite to 35wt % binder). The operating conditions included a hydrogen pressure of2400 psig, a treat gas rate of 5000 scf/b, a dewaxing temperature of658° F. (348° C.), a dewaxing catalyst space velocity of 1.0 hr ⁻¹, anaromatic saturation temperature of 460° F. (238° C.), and an aromaticsaturation catalyst space velocity of 1.0 hr⁻¹. The properties of the560° C.+ portion of the catalytically dewaxed effluent are shown inTable 9. Properties for a raffinate fraction and an extract fractionderived from the catalytically dewaxed effluent are also shown.

TABLE 9 Catalytically dewaxed effluent Product Fraction 560° C.+Raffinate CDW effluent (yield 92.2%) Extract API 30.0 30.2 27.6 VI 104.2105.2 89 KV @100° C. 29.8 30.3 29.9 KV @40° C. 401 405 412 Pour Pt (°C.) −21 −30 Cloud Pt (° C.) 7.8 −24

Although the catalytically dewaxed effluent product was initially clear,haze developed within 2 days. Solvent dewaxing of the catalyticallydewaxed effluent product in Table 9 did not reduce the cloud pointsignificantly (cloud after solvent dewaxing of 6.5° C.) and removed onlyabout 1 wt % of wax, due in part to the severity of the prior catalyticdewaxing. However, extracting the catalytically dewaxed product shown inTable 9 with n-methyl pyrrolidone (NMP) at a solvent/water ratio of 1and at a temperature of 100° C. resulted in a clear and bright productwith a cloud point of −24° C. that appeared to be stable against hazeformation. The extraction also reduced the aromatics content of thecatalytically dewaxed product from about 2 wt % aromatics to about 1 wt% aromatics. This included reducing the 3-ring aromatics content of thecatalytically dewaxed effluent (initially about 0.2 wt %) by about 80%.This result indicates a potential relationship between waxy hazeformation and the presence of polynuclear aromatics in a bright stock.

Example 6

A feed similar to Example 5 were processed in a configuration similar toFIG. 2, with various processing conditions were modified. The initialhydroprocessing severity was reduced relative to the conditions inExample 5 so that the initial hydroprocessing conversion was 59 wt %relative to 510° C. and 34.5 wt % relative to 370° C. These lowerconversions were achieved by operating the demetallization catalyst at739° F. (393° C.) and the hydrotreating/hydrocracking catalystcombination at 756° F. (402° C.).

The hydroprocessed effluent was separated to separate fuels boilingrange fraction(s) from the 370° C.+ portion of the hydroprocessedeffluent. The 370° C.+ portion was then treated in a secondhydroprocessing stage over the hydrocracking catalyst, and dewaxingcatalyst described in Example 4. Additionally, a small amount of ahydrotreating catalyst (hydrotreating catalyst LHSV of 10 hr⁻¹) wasincluded prior to the hydrocracking catalyst, and the feed was exposedto the hydrotreating catalyst under substantially the same conditions asthe hydrocracking catalyst. The reaction conditions included a hydrogenpressure of 2400 psig and a treat gas rate of 5000 scf/b. In a firstrun, the second hydroprocessing conditions were selected to under dewaxthe hydroprocessed effluent. The under-dewaxing conditions correspondedto a hydrocracking temperature of 675° F. (357° C.), a hydrocrackingcatalyst LHSV of 1.2 hr⁻¹, a dewaxing temperature of 615° F. (324° C.),a dewaxing catalyst LHSV of 1.2 hr⁻¹, an aromatic saturation temperatureof 460° F. (238° C.), and an aromatic saturation catalyst LHSV of 1.2hr⁻¹. In a second run, the second hydroprocessing conditions wereselected to more severely dewax the hydroprocessed effluent. The higherseverity dewaxing conditions corresponded to a hydrocracking temperatureof 675° F. (357° C.), a hydrocracking catalyst LHSV of 1.2 hr⁻¹, adewaxing temperature of 645° F. (340° C.), a dewaxing catalyst LHSV of1.2 hr ⁻¹, an aromatic saturation temperature of 460° F. (238° C.), andan aromatic saturation catalyst LHSV of 1.2 hr ⁻¹. The 510° C.+ portionsof the catalytically dewaxed effluent are shown in Table 10.

TABLE 10 Catalytically dewaxed effluents Product Fraction Under-dewaxedHigher severity VI 106.6 106.4 KV @100° C. 37.6 30.5 KV @40° C. 551 396Pour Pt (° C.) −24 −24 Cloud Pt (° C.) 8.6 4.9

Both samples in Table 10 were initially bright and clear, but a hazedeveloped in both samples within one week. Both samples were solventdewaxed under the conditions described in Example 4. This reduced thewax content of the under-dewaxed sample to 6.8 wt % and the wax contentof the higher severity dewaxing sample to 1.1 wt %. The higher severitydewaxing sample still showed a slight haze. However, the under-dewaxedsample, after solvent dewaxing, had a cloud point of −21° C. andappeared to be stable against haze formation.

Example 7 Viscosity and Viscosity Index Relationships

FIG. 4 shows an example of the relationship between processing severity,kinematic viscosity, and viscosity index for lubricant base stocksformed from a deasphalted oil. The data in FIG. 4 corresponds tolubricant base stocks formed form a pentane deasphalted oil at 75 wt %yield on resid feed. The deasphalted oil had a solvent dewaxed VI of75.8 and a solvent dewaxed kinematic viscosity at 100° C. of 333.65.

In FIG. 4, kinematic viscosities (right axis) and viscosity indexes(left axis) are shown as a function of hydroprocessing severity (510°C.+ conversion) for a deasphalted oil processed in a configurationsimilar to FIG. 1, with the catalysts described in Example 1. As shownin FIG. 4, increasing the hydroprocessing severity can provide VI upliftso that deasphalted oil can be converted (after solvent dewaxing) tolubricant base stocks. However, increasing severity also reduces thekinematic viscosity of the 510° C.+ portion of the base stock, which canlimit the yield of bright stock. The 370° C.-510° C. portion of thesolvent dewaxed product can be suitable for forming light neutral and/orheavy neutral base stocks, while the 510° C.+ portion can be suitablefor forming bright stocks and/or heavy neutral base stocks.

Example 8 Variations in Sweet and Sour Hydrocracking

In addition to providing a method for forming Group II base stocks froma challenged feed, the methods described herein can also be used tocontrol the distribution of base stocks formed from a feed by varyingthe amount of conversion performed in sour conditions versus sweetconditions. This is illustrated by the results shown in FIG. 5.

In FIG. 5, the upper two curves show the relationship between the cutpoint used for forming a lubricant base stock of a desired viscosity(bottom axis) and the viscosity index of the resulting base stock (leftaxis). The curve corresponding to the circle data points representsprocessing of a C₅ deasphalted oil using a configuration similar to FIG.2, with all of the hydrocracking occurring in the sour stage. The curvecorresponding to the square data points corresponds to performingroughly half of the hydrocracking conversion in the sour stage and theremaining hydrocracking conversion in the sweet stage (along with thecatalytic dewaxing). The individual data points in each of the uppercurves represent the yield of each of the different base stocks relativeto the amount of feed introduced into the sour processing stage. It isnoted that summing the data points within each curve shows the sametotal yield of base stock, which reflects the fact that the same totalamount of hydrocracking conversion was performed in both types ofprocessing runs. Only the location of the hydrocracking conversion (allsour, or split between sour and sweet) was varied.

The lower pair of curves provides additional information about the samepair of process runs. As for the upper pair of curves, the circle datapoints in the lower pair of curves represent all hydrocracking in thesour stage and the square data points correspond to a split ofhydrocracking between sour and sweet stages. The lower pair of curvesshows the relationship between cut point (bottom axis) and the resultingkinematic viscosity at 100° C. (right axis). As shown by the lower pairof curves, the three cut point represent formation of a light neutralbase stock (5 or 6 cSt), a heavy neutral base stock (10-12 cSt), and abright stock (about 30 cSt). The individual data points for the lowercurves also indicate the pour point of the resulting base stock.

As shown in FIG. 5, altering the conditions under which hydrocracking isperformed can alter the nature of the resulting lubricant base stocks.Performing all of the hydrocracking conversion during the first (sour)hydroprocessing stage can result in higher viscosity index values forthe heavy neutral base stock and bright stock products, while alsoproducing an increased yield of heavy neutral base stock. Performing aportion of the hydrocracking under sweet conditions increased the yieldof light neutral base stock and bright stock with a reduction in heavyneutral base stock yield. Performing a portion of the hydrocrackingunder sweet conditions also reduced the viscosity index values for theheavy neutral base stock and bright stock products. This demonstratesthat the yield of base stocks and/or the resulting quality of basestocks can be altered by varying the amount of conversion performedunder sour conditions versus sweet conditions.

Example 9 Feedstocks and DAOs

Table 1 shows properties of two types of vacuum resid feeds that arepotentially suitable for deasphalting, referred to in this example asResid A and Resid B. Both feeds have an API gravity of less than 6, aspecific gravity of at least 1.0, elevated contents of sulfur, nitrogen,and metals, and elevated contents of carbon residue and n-heptaneinsolubles.

TABLE 11 Resid Feed Properties Resid (566° C.+) Resid A Resid B APIGravity (degrees) 5.4 4.4 Specific Gravity (15° C.) (g/cc) 1.0336 1.0412Total Sulfur (wt %) 4.56 5.03 Nickel (wppm) 43.7 48.7 Vanadium (wppm)114 119 TAN (mg KOH/g) 0.314 0.174 Total Nitrogen (wppm) 4760 4370 BasicNitrogen (wppm) 1210 1370 Carbon Residue (wt %) 24.4 25.8 n-heptaneinsolubles (wt %) 7.68 8.83 Wax (Total − DSC) (wt %) 1.4 1.32 KV @ 100°C. (cSt) 5920 11200 KV @ 135° C. (cSt) 619 988

The resids shown in Table 11 were used to form deasphalted oil. Resid Awas exposed to propane deasphalting (deasphalted oil yield<40%) andpentane deasphalting conditions (deasphalted oil yield ˜ 65%). Resid Bwas exposed to butane deasphalting conditions (deasphalted oilyield˜75%). Table 12 shows properties of the resulting deasphalted oils.

TABLE 12 Examples of Deasphalted Oils C₃ DAO C₄ DAO C₅ DAO API Gravity(degrees) 22.4 12.9 12.6 Specific Gravity (15° C.) (g/cc) 0.9138 0.97820.9808 Total Sulfur (wt %) 2.01 3.82 3.56 Nickel (wppm) <0.1 5.2 5.3Vanadium (wppm) <0.1 15.6 17.4 Total Nitrogen (wppm) 504 2116 1933 BasicNitrogen (wppm) 203 <N/A> 478 Carbon Residue (wt %) 1.6 8.3 11.0 KV @100° C. (cSt) 33.3 124 172 VI 96 61 <N/A> SimDist (ASTM D2887) ° C.  5wt % 509 490 527 10 wt % 528 515 546 30 wt % 566 568 588 50 wt % 593 608619 70 wt % 623 657 664 90 wt % 675 <N/A> <N/A> 95 wt % 701 <N/A> <N/A>

As shown in Table 12, the higher severity deasphalting provided bypropane deasphalting results in a different quality of deasphalted oilthan the lower severity C₄ and C₅ deasphalting that was used in thisexample. It is noted that the C₃ DAO has a kinematic viscosity @100° C.of less than 35, while the C₄ DAO and C₅ DAO have kinematic viscositiesgreater than 100, The C₃ DAO also generally has properties more similarto a lubricant base stock product, such as a higher API gravity, a lowermetals content/sulfur content/nitrogen content, lower CCR levels, and/ora higher viscosity index.

Example 10 Deasphalting of Wide Cut Gas Oil

Performing deasphalting with C₅₊ paraffins can potentially allow forgreater yields of deasphalted oil. However, using a C₅₊ paraffin ormixture of paraffins can pose challenges with regard to the flowproperties of a resid type feed in a deasphalting system. In order tomaintain desirable flow rates/flow properties during deasphalting of aresid type feed, deasphalting processes are typically performed attemperatures of about 190° C. or higher. At such temperatures, the smallparaffins used as deasphalting solvents are gases. As a result, thesolubility of deasphalting solvents tends to decrease with increasingtemperature. When higher yields of deasphalted oil are desired, such asyields of about 60% or more relative to the weight of a resid type feed,the deasphalting solvent may not have sufficient solubility in the residtype feed at 190° C. or higher to generate a desired yield ofdeasphalted oil.

One option for increasing the yield can be to lower the temperature ofthe deasphalting process, which can increase the solubility of thedeasphalting solvent and allow for greater yield. However, such atemperature decrease can also modify the flow properties of the residtype feed, which may result in difficulties with maintaining a flow ofresid type feed through the deasphalting unit.

It has been determined that using a wide cut vacuum gas oil (VGO) thatincludes both resid boiling range compounds and a portion of vacuum gasoil boiling range compounds can mitigate difficulties related tocompatibility of the deasphalting solvent when attempting to generate ahigh yield of deasphalted oil. For example, instead of using a residwith an initial boiling point between 430° C. and 450° C., a wide cutVGO with an initial boiling point of about 370° C. can be used. This canallow a desired yield of deasphalted oil to be generated while stillmaintaining a desired temperature for a deasphalting column.

Table 13 shows results from deasphalting a resid type feed usingn-pentane as the deasphalting solvent at two different yields ofdeasphalted oil. In order to increase the yield of deasphalted oil from65 wt % to 75 wt % (relative to the weight of the feed), thedeasphalting temperature was decreased from 375° F. (190° C.) to 355° F.(˜179° C.). Although this resulted in increased yield of deasphaltedoil, the properties of the higher yield deasphalted oil were lessfavorable. For example, the sulfur content, n-heptane insoluble content,conradson carbon residue, and metals were all higher in the deasphaltedoil at 75 wt % yield relative to the deasphalted oil at 65 wt % yield.

TABLE 13 Deasphalter Yield versus Deasphalter Temperature 355° F. (180°C.) 375° F. (190° C.) 75% Lift 65% Lift Parameter Vac Resid DAO Rock DAORock Density 1.039-1.044  0.989 1.13-1.14 0.98 1.093 (g/ml) Sulfur4.3-4.6 3.7-3.9 7.4-7.7 3.46 8 (wt %) Nitrogen 3750-4380 2500-27006700-7600 2527 6100 (wppm) n-heptane  12 0.23  55 0.04 40 insolubles (wt%) CCR (wt %) 23-25 13.3-13.4 46.4-54.7 10.9 47 Ni + V 145-180 28-29430-540 17.8 380 (wppm) Viscosity @ 4600-7700 230-260 * 173 * 100° C.(cSt) IBP (° C.) 440 430    551 400 526

The results in Table 13 are based on deasphalting of a vacuum residformed by distillation of a feed. In Table 14, deasphalting wasperformed on a wide cut VGO formed by distillation of the same feed. Byincluding a portion of vacuum gas oil in the feed to deasphalting, ayield of 75 wt % deasphalted oil was achieved at 375° F. (190° C.).Additionally, the resulting deasphalted oil had properties that werecloser in nature to the 65 wt % yield deasphalted oil in Table 13. Thisdemonstrates that having a wider cut on the feedstock allowed a higherquality deasphalted oil to be produced at a higher deasphalted oilyield.

TABLE 14 Deasphalting of Wide Cut VGO 375° F. (190° C.) Wide Cut 75%Lift Parameter VGO DAO Rock Density (g/ml) 1.027 0.976 1.139 Sulfur (wt%) 4 3.41 6.89 Nitrogen 3300 2453 6900 (wppm) n-heptane 11.2 0.09 44insolubles (wt %) CCR (wt %) 22 10 49.7 Ni + V (wppm) 133 17.9 378Viscosity @ 5100 112 * 100° C. (cSt) IBP (° C.) 360 285 550

Another benefit of using a wide cut VGO can be related to use ofalternative types of solvents. For example, various refinery processescan potentially generate output streams containing mixtures of C₅compounds. Table 15 shows examples of a first naphtha distillation cutmostly corresponding to isopentane and a second C₅ distillation cut thatcan be generated from the effluent of a naphtha distillation unit.Optionally, a mixed C₅ stream such as the right hand column in Table 15could be distilled to avoid inclusion of benzene. Converting the mixedcompositions of Table 15 into a relatively pure isopentane stream orn-pentane stream for use as a deasphalting solvent can requiresubstantial additional cost. It would be beneficial from both a cost andadditional equipment standpoint if the mixed C₅ compositions of Table 15could be used as a deasphalting solvent, instead of a pure solvent suchas n-pentane or isopentane.

TABLE 15 Mixed C5 Compositions iC5 (wt %) mC5 (wt %) Isobutene 0.1 0Butane 6.4 0.8 2-methylbutane (iC5) 90.0 23.8 Pentane (nC5) 3.5 37.02-methylpentane (iC6) 0 22.2 Hexane (nC6) 0 10.5 Heptane 0 0.1 Octane 00 Cyclopentane 0 2.4 Cyclohexane 0 1.0 Cycloheptane 0 0 Benzene 0 2.1Methylbenzene 0 0.1

One conventional difficulty with using a mixed composition as adeasphalting solvent can be the reduced deasphalting temperaturerequired to generate a desired yield. Table 16 shows the deasphalted oilyield as a function of deasphalting temperature for n-pentane andiso-pentane under conditions similar to those used for deasphalting inTables 13 and 14. As shown in Table 16, the required temperature forgenerating a desired yield with iso-pentane is substantially lower thanthe corresponding temperature for n-pentane. A similar proportionalreduction in the deasphalting temperature would be expected if, forexample, if one of the mixed C₅ streams from Table 15 was used as adeasphalting solvent. However, using a wide cut VGO as the feed fordeasphalting can offset or mitigate the reduction in temperature that isrequired for a desired yield of deasphalted oil.

TABLE 16 Deasphalting Lifts with n-Pentane and Isopentane Lift (lv %)nC5 Temp (° C.) iC5 Temp (° C.) 75 180 154 70 188 171 65 191 178

Example 11 Yield Comparison of Product Types

The methods described herein can provide advantages for convertingdeasphalted oils to higher value products. Traditionally, vacuum residfractions have been processed using severe types of processing, such ascoking or slurry hydroconversion. Table 17 shows examples of typicalproduct yields that might be expected based on coking or slurryhydroconversion of a resid feed.

TABLE 17 Thermal Cracking and Slurry Hydroconversion Yields DelayedCoker FlexiCoker Slurry HDC (vol %) (vol %) (vol %) Gas, foe 9% 16% 15%Naphtha 16% 18% 19% Diesel 24% 19% 50% Lube Base stocks 0% 0% 0% Gasoil(371° C.+) 28% 24% 27% Heavy Gasoil/Coke/ 29% 24% 7% Pitch (566° C.+)

As shown in Table 17, coking of a resid feed tends to producesubstantial amounts of coke. Coke is a low value product that haslimited uses other than fuel value. In addition to transforming roughly25% of the feed to coke, coking also generates a gas oil fraction whichis generally not considered to be suitable for use as a lubricant basestock. Instead, the gas oil generated by coking is generally used as afuel oil, or is used as a feed for fluid catalytic cracking. Slurryhydroconversion generates a smaller amount of low value pitch and/orheavy gas oil, and also can directly produce a higher proportion ofdiesel fuel. However, slurry hydroconversion can also requiresubstantial amounts of hydrogen, so the operating costs that arerequired to perform slurry hydroconversion may not be justified based onthe resulting diesel yield.

In contrast to traditional methods, deasphalting a resid followed byprocessing as described herein can produce a higher value product slate.Table 18 shows an example of product slates formed from the C₄ DAO andC₅ DAO shown in Table 12.

TABLE 18 Deasphalting and Lubes Processing Yields C₄ DAO HDC C₅ DAO HDC(vol %) (vol %) Gas, foe 2% 2% Naphtha 9% 16% Diesel 29% 37% Lube Basestocks 35% 35% Gasoil (371° C.+) 0% 0% Heavy Gasoil/Coke/ 35% 25% Pitch(566° C.+)

As shown in Table 18, deasphalting of a resid initially forms asubstantial amount of pitch or rock as a product, depending on thedeasphalting conditions. However, substantially all of the desasphaltedoil can then be converted to higher value products, such as the 35 vol %of lubricant base stocks that is shown in Table 18. The amount of lightends produced by deasphalting and lubes processing is also substantiallylower than the light ends production from coking or slurryhydroconversion.

Example 12 Lubricant Base Stocks from Catalytic Processing of C₄Deasphalted Oil

A configuration similar to FIG. 6 was used to form lubricant base stocksfrom deasphalted oil formed by propane deasphalting. FIG. 7 showscompositional details for examples of bright stocks that were producedfrom catalytic processing of C₃ deasphalted oils (Samples I and II inFIG. 7). FIG. 7 also shows two reference bright stocks formed by eithersolvent dewaxing or catalytic dewaxing (Ref 1 and Ref 2), and anadditional bright stock formed from a C₃ deasphalted oil (Sample III),but with a high cloud point of 6° C.

For the bright stocks shown as Samples I and II in FIG. 7, the brightstocks were formed by hydrotreatment (sour conditions) followed bycatalytic dewaxing (sweet conditions) of the C₃ deasphalted oil. SamplesI and II in FIG. 7 correspond to a bright stocks with less than 0.03 wt% sulfur and less than 10 wt % aromatics/greater than 90 wt % saturates.Thus, Samples I and II correspond to Group II bright stocks. Thereference bright stocks in the first two columns of FIG. 7, as well asSample III, also have less than 10 wt % aromatics/greater than 90 wt %saturates and therefore also correspond to Group II bright stocks.

The compositional characterization was done using ^(—)C-NMR, FDMS (FieldDesorption Mass Spectrometry), FTTCR-MS (Fourier-Transform Ion CyclotronResonance Mass Spectrometry), and DSC (Differential ScanningCalorimetry). The differences in composition include the inventive basestocks having a higher degree of branching than a conventional brightstock. For example, the sum of the propyl and ethyl groups (Line 9) isgreater than 1.7, or 1.8, or 1.9 per 100 carbon atoms in Samples I andII. Additionally, in Samples I and II, the types of individual branchingare higher than their references. Samples I and II show a total numberof terminal/pendant propyl groups greater than 0.85, or greater than0.86, or greater than 0.90 per 100 carbon atoms; they show a totalnumber of ethyl groups greater than 0.85, or greater than 0.88, orgreater than 0.90, or greater than 0.93, or greater than 0.95 per 100carbon atoms. Additionally, although not shown in FIG. 7. Samples I andII have a total number alpha carbon atoms greater than 2.1, or greaterthan 2.2, or greater than 2.22, or greater than 2.3 per 100 carbonatoms.

Further, the inventive base stocks exhibited more external branchingwithin paraffinic chains. For Samples I and II, the total number ofpropyl and ethyl groups relative to epsilon carbon atoms was greaterthan 0.127, or greater than 0.130, or greater than 0.133, or greaterthan 0.140, or greater than 0.150 or greater than 0.160. Similarly, theratio of propyl groups to epsilon carbon atoms was greater than 0.063 orgreater than 0.065, and the ratio of ethyl groups to epsilon carbonatoms was greater than 0.064, or greater than 0.065, or greater than0.068, or greater than 0.070, respectively. Additionally, although notshown in FIG. 7, the ratio of alpha carbons to the sum of propyl andethyl groups is smaller in Samples I and II: less than 1.36, or lessthan 1.3, or less than 1.25, or less than 1.24.

Still other differences in the composition of Samples I and II over thereferences can be seen in the distribution of cycloparaffinic species asdetermined by FDMS. For example, the inventive bright stocks have atleast 20% (i.e., at least 20 molecules per 100 molecules of thecomposition) of 2-ring cycloparaffins; at least 22% (i.e., at least 22molecules per 100 molecules of the composition) of 3-ringcycloparaffins; less than 13.5% (i.e., less than 13.5 molecules per 100molecules of the composition) of 5-ring cycloparaffins and less than8.5% (i.e., less than 8.5 molecules per 100 molecules of thecomposition), or less than 8.0 molecules per 100 molecules, or less than7.0 molecules per 100 molecules, of 6-ring cycloparaffins. Comparing theratio of 1, 2, and 3 ring cycloparaffins to 4, 5, and 6 ringcycloparaffins, differences are observed in that the ratio in Samples Iand II is at least 1.1. Additionally, the ratio of 5 and 6 ringcycloparaffins to 2 and 3 ring cycloparaffins is less than 0.58, or lessthan 0.57.

Also, the inventive oils were also characterized using differentialscanning calorimetry (DSC) to determine the total amount of residual waxand the distribution of residual wax as a function of temperature. TheDSC cooling and heating curves were obtained for the base stocksdescribed herein. Notably, the heating curve was generated by startingfrom a low temperature of nearly −80° C., at which point the sample iscompletely solidified, and then heating the sample at rate of about 10°C./min. As the temperature increases, typically, the heat flow rapidlydecreases and reaches a minimum at around −20° C. to −10° C. Between−20° C. and abound +10° C., the rate of heat flow increases as themicrocrystalline wax melts. The typical rate of increase found in thereferences ranged from 0.00068 to 0.013 W/g-° C. whereas column 4 had aless rapid change in heat flow at a rate of 0.00042 W/g-° C., indicativeof a novel composition and distribution of waxy species.

It was determined that the novel product composition space shown in FIG.7 could be achieved using catalytic processing of C₃ deasphalted oilhaving a VI of about 96, a CCR of about1.6 wt %, and with nitrogen ofabout 504 ppmw. It has further been found that a similar novel productcomposition space can be achieved with more challenging feedstocks suchas base stocks produced from C₄ deasphalted oil or from C₅ deasphaltedoil or from C₆₊ deasphalted oil or from mixtures thereof. This isillustrated in FIG. 8, where base stock compositions are shown thatderived from C₄ deasphalted oil (55-65% deasphalted oil yield). The basestocks shown were produced using catalytic processing with and withoutsolvent post-processing steps. There is an increased risk of theappearance of haze in the final product if the stock does not occupy thecompositional space described below. Samples IV and V in FIG. 8correspond to base stocks that remained clear and bright, while SamplesVI, VII, and VIII correspond to base stocks that developed a haze, aswould be conventionally expected when attempting to form base stocksfrom a C₄₊ DAO. Ref 1 and Ref 2 in FIG. 8 are the same as the referencesin FIG. 7.

The compositional characterization was done using 13C-NMR, FDMS,FTICR-MS, and DSC. The differences in composition include the inventivebase stocks having a higher degree of branching than a conventionalbright stock. For example, the sum of the terminal/pendant propyl andethyl groups is greater than 1.7, or 1.75, or 1.8, or 1.85, or 1.9 per100 carbon atoms in Samples IV and V. Additionally, in Samples IV and V,the types of individual branching are higher than the references.Specifically, Samples IV and V show a total number of terminal/pendantpropyl groups greater than 0.86, or greater than 0.88 per 100 carbonatoms; they also show a total number of terminal/pendant ethyl groupsgreater than 0.88, or greater than 0.90, or greater than 0.93, orgreater than 0.95 per 100 carbon atoms. Although not shown in FIG. 8,Samples IV and V also had a total number alpha carbon atoms of 2.3 orgreater per 100 carbon atoms.

Further, the inventive base stocks exhibited more external branchingwithin paraffinic chains. For Samples IV and V, the total number ofpropyl and ethyl groups relative to epsilon carbon atoms was greaterthan 0.124, or greater than 0.127, or greater than 0.130, or greaterthan 0.133. Similarly, the ratio of propyl groups to epsilon carbonatoms and the ratio of ethyl groups to epsilon carbon atoms was greaterthan 0.060 or greater than 0.063 or greater than 0.064 or greater than0.065, and 0.064 or greater than 0.065, or greater than 0.068,respectively.

FDMS provides more information concerning the ring structures in theinventive bright stocks. Samples IV and V show increased prevalence of1, 2 and 3 ring cycloparaffins and decreased prevalence of 4, 5 and 6ring cycloparaffins. For example, Samples IV and V have at least 10.7%(i.e., at least 10.7 molecules per 100 molecules of the composition), orat least 11%, or at least 11.5%, or at least 11.9% 1 ringcycloparaffins; and at least 19.8%, or at least 20% (i.e., at least 20.0molecules per 100 molecules of the composition), or at least 20.5%, orat least 20.8% 2 ring cycloparaffins; at least 21.8%, or at least 21.9%,or at least 22% (i.e., at least 22.0 molecules per 100 molecules of thecomposition) 3 ring cycloparaffins; less than 17.6% (i.e., less than17.6 molecules per 100 molecules of the composition), or less than17.5%, or less than 17.1%, or less than 17% 4 ring cycloparaffins; lessthan 11.9% (i.e., less than 11.9 molecules per 100 molecules of thecomposition), or less than 11.5%, or less than 11%, or less than 10.9% 5ring cycloparaffins; and less than 7.2%, or less than 7% (i.e., lessthan 7.0 molecules per 100 molecules of the composition), or less than6.5%, or less than 6.3% 6 ring cycloparaffins. Comparing the ratio of 1,2, and 3 ring cycloparaffins to 4, 5, and 6 ring cycloparaffins,differences are observed in that the ratio in Samples IV and V is atleast 1.41, or at least 1.45, or at least 1.5, or at least 1.55, or atleast 1.59 (line 68). Samples IV and V also show a ratio of 5 and 6 ringcycloparaffins to 2 and 3 ring cycloparaffins of 0.40 or less.

Example 13 Lubricant Base Stocks from Catalytic Processing of C₅Deasphalted Oil

FIGS. 9 and 10 provide details from characterization of various basestock compositions that were formed from C₅ deasphalted oils. FIG. 9shows properties determined using various techniques, including ¹³C-NMR,while FIG. 10 shows properties determined using FTICR-MS and FDMS. Ref 1is the same as Ref 1 from FIGS. 7 and 8. Samples A, B, and C correspondto novel compositions, while Samples D, E, F, and G correspond toadditional comparative base stocks made from C₅ deasphalted oil.

The compositional characterization was done using ¹³C-NMR, FDMS,FTICR-MS, and DSC. The differences in composition include the inventivebase stocks having a higher degree of branching than a conventionalbright stock as observed using NMR. For example, as shown FIG. 9, thecomparative and reference bright stocks have a sum of terminal/pendantpropyl and terminal/pendant ethyl groups of 1.67 (or less) per 100carbon atoms in the composition. By contrast, the inventive brightstocks have a value of at least 1.7 or at least 1.8, or at least 1.9, orat least 2, or at least 2.2 per 100 carbons. Similarly, individualvalues for terminal/pendant propyl and ethyl groups for thereference/comparative bright stocks are 0.84 or less and 1.04 or less(respectively) per 100 carbons. The inventive bright stocks (Samples A,B, and C) have values of at least 0.85, or at least 0.9 or at least 1.0per 100 carbons for propyl groups and at least 0.85, or at least 1.0, orat least 1.1, or at least 1.15, or at least 1.2 per 100 carbons forethyl groups. Further, although not shown in FIG. 12, the branch pointsof Samples A, B, and C are characterized by have a total branch pointsof at least 4.1 per 100 carbon atoms and of those branch points, lessthan 2.8 per 100 carbons are alpha carbons.

Samples A, B, and C showed more external branching within paraffinicchains as seen when comparing the ratios of various branch points toepsilon carbons. Comparing the ratio of the sum of propyl and ethylgroups to the epsilon carbons indicates a higher degree of branching inthe inventive bright stocks. The reference/comparative bright stockshave a ratio of less than 0.13 for the sum of ethyl and propyl groupsrelative to the number of epsilon carbons, while the inventive brightstocks have at least 0.1, or at least 0.13, or at least 0.14, or atleast 0.15, or at least 0.16 or at least 0.19 for the sum of ethyl andpropyl groups to epsilon carbons. Individually comparing propyl or ethylgroups to epsilon carbons shows a similar relationship with referencebright stocks having less than 0.058 and 0.059 respectively. Samples A,B, and C have values of at least 0.06, or at least 0.07, or at least0.08 or at least 0.09 for propyl/epsilon and at least 0.06, or at least0.07, or at least 0.08, or at least 0.1 for ethyl/epsilon. Additionally,the total number of epsilon carbons is lower in the inventive brightstocks: greater than 14.5 for the reference/comparative bright stocksand less than 14.5, or less than 13, or less than 12.5, or less than12.35 or less than 11 for the inventive bright stocks.

Although not shown in FIG. 9, the proportion of the type of branchpoints is also unique in the inventive bright stocks. The reference basestocks have a ratio of alpha carbons to ethyl groups of at least 2.8 anda ratio of alpha carbons to the sum of ethyl and propyl groups of atleast 1.8. The inventive bright stocks have a ratio of alpha carbons toethyl groups of less than 2.6, or less than 2.54, or less than 2.5, orless than 2.2 or less than 2 and a ratio of alpha carbons to the sum ofethyl and propyl groups of less than 2, or less than 1.4, or less than1.38, or less than 1.3, or less than 1.1, or less than 1 or less than0.9. Similarly the proportion of propyl and ethyl groups to total branchpoints is less than 0.41 for the reference/comparative bright stocks andat least 0.39, or at least 0.4, or at least 0.42, or at least 0.43, orat least 0.45, or at least 0.46 or at least 0.48 for the inventivebright stocks with the alpha carbons making up the remainder of branchpoints at a proportion of at least 0.59 for the reference/comparativebright stocks and less than 0.58, or less than 0.57, or less than 0.56,or less than 0.55 or less than 0.52 for the inventive bright stocks.

Another difference in the composition of the inventive bright stocks isthe cycloparaffinic distribution as measured by FTICR-MS and/or FDMS, asshown in FIG. 10. These measurements indicate that the inventive brightstocks have a higher number of molecules with 2 rings: less than 18.01per 100 molecules for the reference/comparative bright stocks and atleast 17.0, or at least 18.01, or at least 18.5, or at least 19, or atleast 20 (i.e., at least 20.0 molecules per 100 molecules of thecomposition), or at least 20.07 per 100 molecules for Samples A, B, andC. Molecules with 3 rings follow a similar trend with less than 19.7 per100 molecules for the reference/comparative bright stocks and at least19.7, or at least 20 (i.e., at least 20.0 molecules per 100 molecules ofthe composition), or at least 20.5 or at least 20.62 per 100 moleculesfor the inventive bright stocks. Molecules with 6, 7 or 8 rings followthe opposite trend with fewer of these molecules in the inventive brightstocks with at least 7.2 molecules with 6 rings per 100 molecules in thereference/comparative bright stocks, at least 4.8 molecules with 7 ringsand at least 2.1 molecules with 8 rings. The inventive bright stockshave less than 7.1, or less than 7 (i.e., less than 7.0 molecules per100 molecules of the composition), or less than 6.9 or less than 6.8molecules with 6 rings per 100 molecules; less than 4.2, or less than 4(i.e., less than 4.0 molecules per 100 molecules of the composition), orless than 3.8, or less than 3.6 or less than 3.3 molecules with 7 ringsper 100 molecules; and less than 2 (i.e., less than 2.0 molecules per100 molecules of the composition), or less than 1.9, or less than 1.8 orless than 1.5 molecules with 8 rings per 100 molecules. Additionally theinventive bright stocks have less than 1 (i.e., less than 1.0 moleculesper 100 molecules of the composition), or less than 0.9, or less than0.8, or less than 0.3 molecules with 9 rings per 100 molecules.

Molecules with fewer rings are favored in the inventive bright stockswhen comparing the number of molecules with 5 or more, 6 or more, 7 ormore and 11 or more rings. For example the reference/comparative brightstocks have at least 25.6, 14.9, 7.3 and 0.02 molecules with 5 or more,6 or more, 7 or more and 11 or more rings per 100 molecules,respectively. The inventive bright stocks have less than 25.5, or lessthan 25, or less than 24.5, or less than 24, or less than 23 moleculeswith 5 or more rings per 100 molecules, less than 15, or less than 14.5,or less than 14, or less than 13, or less than 12 molecules with 6 ormore rings per 100 molecules, less than 7.2, or less than 7, or lessthan 6.5, or less than 6, or less than 5 molecules with 7 or more ringsper 100 molecules, and less than 0.02, or less than 0.01 or 0 moleculeswith 11 or more rings per 100 molecules. Additionally, when comparingthe ratio of molecules with at least 5 rings to those with 2 rings, thereference/comparative bright stocks have a ratio of at least 1.5 whereasthe inventive bright stocks have a ratio of less than 1.4, or less than1.3, or less than 1.2. The inventive bright stocks also have smallerratios of molecules with at least 6 rings and molecules with at least 7rings to those with 2 rings: less than 0.9, or less than 0.8, or lessthan 0.7, or less than 0.6 for molecules with at least 6 rings comparesto those with 2 and less than 0.4, or less than 0.3 for molecules withat least 7 rings to those with 2 rings.

The overall distribution of rings demonstrates that the inventive brightstocks favor molecules with fewer number of rings. The reference brightstocks have at least 0.05%, at least 0.08%, at least 2.22%, at least6.14%, at least 16.6% and at least 32.2% molecules with at least 11, atleast 10, at least 8, at least 7, at least 6 and at least 5 rings,respectively. The inventive bright stocks have less than 0.05, or lessthan 0.03 or 0 molecules per 100 with at least 11 rings, less than 0.08,or less than 0.07 or 0 molecules per 100 with at least 10 rings, lessthan 2.2, or less than 2.1, or less than 2, or less than 1.9 or lessthan 1.5, or less than 1 molecule(s) per 100 with at least 8 rings, lessthan 6.5, or less than 4.5, or less than 4, or less than 3, or less than2 per 100 molecules with at least 7 rings, less than 16, or less than15, or less than 14, or less than 13, or less than 12, or less than 11,or less than 10 per 100 molecules with at least 6 rings and less than30, or less than 29, or less than 28, or less than 27 or less than 26,or less than 25 per 100 molecules with at least 5 rings. Thereference/comparative bright stocks also have less than 70 per 100molecules with 4 or fewer rings as compared to the inventive brightstocks which have at least 70, or at least 71, or at least 72 or atleast 74 per 100 molecules with 4 or fewer rings. This lower number oflarge ring species seen in the composition is also reflected in thelower Conradson Carbon Residue (CCR) values for Samples A, B, and C inFIG. 9.

The distribution of number of rings in the inventive bright stocksfavors a lower number of rings. For example, the ratio of 5 and 6 ringmolecules compared to 2 and 3 ring molecules is greater than 0.7 for thereference/comparative bright stocks and less than 0.7, or less than 0.65or less than 0.6 for the inventive bright stocks. The ratio of 2 and 3ring molecules to molecules with 1 ring is also larger in the inventivebright stocks: less than 3.5 per 100 for the reference/comparativebright stocks and at least 3.5, or at least 4 per 100 for the inventive.Additionally, when comparing the ratio of molecules with at least 5rings to those with 3 or few or to those with 4 or fewer, additionaldifferences are observed. The reference/comparative bright stocks have aratio of molecules with at least 5 rings to those with three or fewer ofat least 0.57 and a ratio of molecules with at least 5 rings to thosewith 4 or fewer of less than 0.43. The inventive bright stocks have aratio of molecules with at least 5 rings to those with 3 or fewer ofless than 0.57, or less than 0.55 or less than 0.53 and a ratio ofmolecules with at least 5 rings to those with 4 or fewer of at least0.43, or at least 0.4 or at least 0.38.

Example 14 Heavy Neutral Base Stock Production from C₃ DAO

A deasphalted oil derived from a vacuum resid feed was used to form awide boiling range heavy neutral base stock. A high viscosity vacuumresid feed was processed by propane deasphalting to form deasphalted oiland rock. FIG. 11 shows the properties of the deasphalted oil, as wellas a few additional properties for the deasphalted oil after solventdewaxing to a pour point of −17° C. As shown in FIG. 11, the deasphaltedoil had a kinematic viscosity at 100° C. of 33.2, a VI of roughly 96,and a sulfur content of roughly 2 wt %. The boiling range for thedeasphalted oil included a T5 distillation point of 509° C., a T50distillation point of 593° C., a T95 distillation point of 701° C., anda T99.5 distillation point of 738° C. In addition to FIG. 11, it isnoted that the deasphalted oil included about 60 wt % aromatics. For thesolvent dewaxing, the deasphalted oil was dewaxed using a 50 vol %/50vol % mixture of methyl ethyl ketone and toluene. The solvent to oilratio (vol/vol) was 3 to 1, and the slurry temperature for the solventdewaxing was −20° C. As shown in FIG. 11, the deasphalted oil wassolvent dewaxed to a pour point of −17° C. This resulted in a solventdewaxed DAO with a kinematic viscosity at 100° C. of 40.7 and a VI of85.

The deasphalted oil was processed under conditions similar to those thatcould be used for an initial stage of hydroprocessing for lubricant baseoil production. This included exposing the deasphalted oil sequentiallyto a hydrotreating catalyst, a hydrocracking catalyst, and an aromaticsaturation catalyst in a stacked bed catalyst arrangement. The catalystscorresponded to commercially available NiMo and/or NiMoW catalysts. Theprocessing conditions included a pressure of 2500 prig (17.2 MPag), aliquid hourly space velocity (LHSV) of 0.4 hr⁻¹, and a temperaturebetween 335° C. and 380° C. This range of temperatures corresponded toamounts of conversion relative to 370° C. of about 5 wt % to about 62 wt%.

The total liquid product was then cut into a 370° C.-510° C. fractionand a 510° C.+ fraction. The fractions were then solvent dewaxed tomeasure wax content, dewaxed oil kinematic viscosity, and dewaxed oilviscosity index. Additionally, 370° C.+ viscosities were determined forthe total 370° C.+ fraction based on the values for the 370° C.-510° C.fraction and the 510° C.+ fraction.

FIG. 11 shows the resulting viscosities and VI values for the solventdewaxed oils as function of 370° C. conversion. As shown in FIG. 12, the370° C.-510° C. fraction had a kinematic viscosity at 100° C. thatranged from 8 cSt to 4 cSt, depending on the amount of feed conversion.The 510° C.+ portion had a much larger variation, with kinematicviscosities of nearly 30 cSt down to 10 cSt, depending on the amount ofconversion. The viscosity index for the solvent dewaxed oils was similarfor both the 370° C.-510° C. and the 510° C.+ portions, with the 510°C.+ VI values generally being 5-10 greater than the VI values for thecorresponding 370° C.-510° C. portion.

For formation of a heavy neutral base stock, the hydroprocessed effluentfrom a run with 9 wt % conversion relative to 370° C. was selected forfurther processing. After separation, the 370° C.+ portion of the firsthydroprocessing stage effluent had a sulfur content of 21 wppm, anitrogen content of less than 1 wpm, and a kinematic viscosity at 100°C. of 20 cSt. It is noted that the conversion across the firsthydroprocessing stage was less than 15 wt % relative to 370° C. As aresult, additional conversion was performed in the secondhydroprocessing stage in order to produce a final 370° C.+ fraction witha kinematic viscosity at 100° C. of 16 cSt or less.

The 370° C.+ portion of the first hydroprocessed effluent was thenprocessed in a second catalytic processing stage. The catalysts includedin the second catalytic processing stage were a) a commerciallyavailable noble metal hydrotreating catalyst, b) a dewaxing catalystincluding 0.6 wt % Pt supported on 65 wt % ZSM-48 (70:1 silica toalumina ratio)/35 wt % alumina binder, and c) an aromatic saturationcatalyst including 0.6 wt % Pt supported on 65 wt % MCM-41/35 wt %alumina binder. The aromatic saturation catalyst was included in aseparate reactor from the hydrotreating and dewaxing catalysts, to allowfor separate temperature control for the aromatic saturation. Thedewaxing temperature across the catalytic dewaxing catalyst was variedbetween 329° C. and 343° C. The hydrotreating temperature was selectedto provide a total conversion across the hydrotreating/dewaxing reactorof 82-89 wt %, depending on the dewaxing temperature. Other conditionsin the hydrotreating/dewaxing reactor included a total pressure of 2500psig (17.2 MPag) and a LHSV of 0.6.

The resulting second hydroprocessing stage effluent was then separatedto remove light ends and fuel boiling range components, followed byseparation to form a heavy neutral cut and a bright stock cut. The heavyneutral cut had a kinematic viscosity at 100° C. of 11-12 cSt while thebright stock had a kinematic viscosity at 100° C. of 29-31 cSt. Thebright stocks also had cloud points of −13° C. to 6° C., depending onthe temperature of the catalytic dewaxing. Based on these values, it wascalculated that the total 370° C.+ portions (prior to cutting to formheavy neutral and a bright stock cuts) had kinematic viscosities of16.1-17.8 cSt at 100° C. It was also calculated based on pour pointblending that the pour point of the 370° C.+ fraction was between −36°C. and −22° C., depending on the dewaxing temperature. The VI of the370° C.+ fraction was 105-106. Based on these values, it appeared thatthe 370° C.+ portion of the second hydroprocessed effluent was suitablefor use as a Group II heavy neutral base stock without furtherseparation into cuts and/or without further processing. It is noted thatoperating the first hydroprocessing stage at higher severity resulted inlower viscosity products. Thus, if desired, additional conversion in thefirst hydroprocessing stage could be performed to allow for formation ofa lower viscosity 370° C.+ portion, but with a higher VI that couldcorrespond to a Group II, Group II+, Group III, or Group III+ heavyneutral base stock.

Additional Embodiments

Embodiment 1. A method for making lubricant base stock, comprising:performing solvent deasphalting using a C₃ or C₄ solvent under effectivesolvent deasphalting conditions on a feedstock having a T5 boiling pointof at least 400° C. (or at least 450° C., or at least 500° C.), theeffective solvent deasphalting conditions producing a yield ofdeasphalted oil of 40 wt % or less (or 35 wt % or less, or 30 wt % orless) of the feedstock; hydroprocessing at least a portion of thedeasphalted oil under first effective hydroprocessing conditions to forma hydroprocessed effluent having a sulfur content of 300 wppm or less(or 100 wppm or less) and a nitrogen content of 100 wppm or less, the atleast a portion of the deasphalted oil having an aromatics content of atleast about 50 wt %; separating the hydroprocessed effluent to form atleast a fuels boiling range fraction and a bottoms fraction; andhydroprocessing at least a portion of the hydroprocessed bottomsfraction under second effective hydroprocessing conditions, the secondeffective hydroprocessing conditions comprising catalytic dewaxingconditions, to form a catalytically dewaxed effluent, wherein thecatalytically dewaxed effluent comprises a 950° F.+ (510° C.+) portionhaving a VI of at least 80, a pour point of −6° C. or less, and a cloudpoint of −2° C. or less.

Embodiment 2. The method of Embodiment 1, wherein the catalyticallydewaxed effluent and or the 510° C.+ portion of the catalyticallydewaxed effluent has a VI of at least 90, or at least 95, or at least100.

Embodiment 3. A method for making lubricant base stock, comprising:performing solvent deasphalting using a C₃ solvent under effectivesolvent deasphalting conditions on a feedstock having a T5 boiling pointof at least 400° C. to produce deasphalted oil and rock, a yield ofdeasphalted oil being 40 wt % or less; hydroprocessing at least aportion of the deasphalted oil under first effective hydroprocessingconditions to form a hydroprocessed effluent, the at least a portion ofthe deasphalted oil having a kinematic viscosity at 100° C. of at least30 cSt, the hydroprocessed effluent having a sulfur content of 50 wppmor less (or 20 wppm. or less) and a nitrogen content of 20 wppm or less(or 5 wppm or less), the first effective hydroprocessing conditionscomprising a first amount of conversion of the at least a portion of thedeasphalted oil relative to 370° C.; separating the hydroprocessedeffluent to form at least a fraction comprising fuels boiling rangeportion and a hydroprocessed bottoms fraction; and hydroprocessing atleast a portion of the hydroprocessed bottoms fraction under secondeffective hydroprocessing conditions to form a catalytically dewaxedeffluent, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions and further comprising a second amount ofconversion of the at least a portion of the hydroprocessed bottomsfraction, a yield of a 370° C.+ portion of the catalytically dewaxedeffluent being at least about 50 wt % relative to the at least a portionof the deasphalted oil, wherein the 370° C.+ portion of thecatalytically dewaxed effluent comprises a VI of at least 100, a pourpoint of −10° C. or less, and a kinematic viscosity at 100° C. of 8 cStto 20 cSt.

4. The method of Embodiment 3, wherein the first effectivehydroprocessing conditions comprising conditions for conversion of 7 wt% to 25 wt % of the at least a portion of the deasphalted oil relativeto a conversion temperature of 370° C., the second effectivehydroprocessing conditions comprising conditions for conversion of 10 wt% to 20 wt % of the at least a portion of the hydroprocessed bottoms.

5. The method of any of Embodiments 3 to 4, further comprisingseparating the catalytically dewaxed effluent under separationconditions comprising a pressure of at least 90 kPaa to form a 370° C.+portion, the separating the hydroprocessed effluent comprisingseparating the hydroprocessed effluent wider separation conditionscomprising a pressure of at least 90 kPaa.

Embodiment 6. The method of any of Embodiments 3 to 5, wherein the 370°C.+ portion of catalytically dewaxed effluent has a VI of at least 105,or at least 110, or at least 120.

Embodiment 7. The method of any of the above embodiments, wherein thecatalytically dewaxed effluent, the 370° C.+ portion of thecatalytically dewaxed effluent, and/or the 510° C.+ portion of thecatalytically dewaxed effluent comprises a saturates content of at least90 wt %, or at least 95 wt %.

Embodiment 8. The method of any of the above embodiments, wherein thecatalytically dewaxed effluent, the 370° C.+ portion of thecatalytically dewaxed effluent, and/or the 510° C.+ portion of thecatalytically dewaxed effluent has a pour point of −10° C. or less, or−15° C. or less, or −20° C. or less; or a cloud point of −10° C. orless, or −15° C. or less; or a combination thereof.

Embodiment 9. The method of any of the above embodiments, wherein thefirst effective hydroprocessing conditions comprise conditions forconversion of 10 wt % to 40 wt % of the at least a portion of thedeasphalted oil relative to a conversion temperature of 510° C., orwherein the first effective hydroprocessing conditions comprisehydrotreating conditions, hydrocracking conditions, aromatic saturationconditions, or a combination thereof.

Embodiment 10. The method of any of the above embodiments, wherein thesecond effective hydroprocessing conditions further comprise a) secondhydrotreating conditions, optionally in the presence of a noble metalhydrotreating catalyst, b) second hydrocracking conditions, optionallyin the presence of a noble metal hydrocracking catalyst, or c) acombination thereof.

Embodiment 11. The method of any of the above embodiments, wherein thesecond effective hydroprocessing conditions further comprise secondaromatic saturation conditions, optionally in the presence of a noblemetal aromatic saturation catalyst.

Embodiment 12. A lubricant composition having a T5 boiling point of atleast 350° C., a T30 boiling point of 427° C. or less, and a T90 boilingpoint of at least 566° C., the lubricant composition comprising a sulfurcontent of 50 wppm or less (or 20 wppm or less), a nitrogen content of20 wppm or less (or 5 wppm or less), a saturates content of at least 90wt %, a VI of at least 100, and pour point of −10° C. or less, and akinematic viscosity at 100° C. of 8 cSt to 20 cSt.

Embodiment 13. The lubricant composition of Embodiment 12, wherein thekinematic viscosity at 100° C. is 8 cSt to 18 cSt, or 8 cSt to 16 cSt,or wherein the lubricant composition has a pour point of −15° C. orless, or −20° C. or less, or wherein the lubricant composition has a VIof at least 105, or at least 110, or at least 120, or a combinationthereof.

Embodiment 14. A catalytically dewaxed effluent produced according toany of Embodiments 1-11.

Embodiment 15. A bright stock formed from the solvent processed effluentof Embodiment 14 or the lubricant composition of any of Embodiments12-13, the bright stock optionally being a Group II bright stock.

Embodiment 16. The lubricant composition of Embodiment 12 or 13, whereinthe lubricant composition further comprises an additive.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present invention,including all features which would be treated as equivalents thereof bythose skilled in the art to which the invention pertains.

The present invention has been described above with reference tonumerous embodiments and specific examples. Many variations will suggestthemselves to those skilled in this art in light of the above detaileddescription. All such obvious variations are within the full intendedscope of the appended claims.

1. A method for making lubricant base stock, comprising: performingsolvent deasphalting using a C₃ or C₄ solvent under effective solventdeasphalting conditions on a feedstock having a T5 boiling point of atleast 370° C., the effective solvent deasphalting conditions producing ayield of deasphalted oil of 40 wt % or less of the feedstock;hydroprocessing at least a portion of the deasphalted oil under firsteffective hydroprocessing conditions to form a hydroprocessed effluenthaving a sulfur content of 300 wppm or less and a nitrogen content of100 wppm or less, the at least a portion of the deasphalted oil havingan aromatics content of at least about 50 wt %; separating thehydroprocessed effluent to form at least a fuels boiling range fractionand a bottoms fraction; and hydroprocessing at least a portion of thehydroprocessed bottoms fraction under second effective hydroprocessingconditions, the second effective hydroprocessing conditions comprisingcatalytic dewaxing conditions, to form a catalytically dewaxed effluent,wherein the catalytically dewaxed effluent comprises a 950° F.+ (510°C.+) portion having a VI of at least 80, a pour point of −6° C. or less,and a cloud point of −2° C. or less.
 2. The method of claim 1, whereinthe catalytically dewaxed effluent comprises a saturates content of atleast 90 wt %.
 3. The method of claim 1, wherein the catalyticallydewaxed effluent has a pour point of −10° C. or less; or a cloud pointof −10° C. or less; or a combination thereof.
 4. The method of claim 1,wherein the second effective hydroprocessing conditions further comprisehydrocracking conditions and/or aromatic saturation conditions.
 5. Themethod of claim 1, wherein the catalytically dewaxed effluent has a VIof at least
 90. 6. The method of claim 1, wherein the first effectivehydroprocessing conditions comprise conditions for conversion of 10 wt %to 40 wt % of the at least a portion of the deasphalted oil relative toa conversion temperature of 510° C.
 7. The method of claim 1, whereinthe first effective hydroprocessing conditions comprise hydrotreatingconditions, hydrocracking conditions, aromatic saturation conditions, ora combination thereof.
 8. A method for making lubricant base stock,comprising: performing solvent deasphalting using a C₃ solvent undereffective solvent deasphalting conditions on a feedstock having a T5boiling point of at least 400° C. to produce deasphalted oil and rock, ayield of deasphalted oil being 40 wt % or less; hydroprocessing at leasta portion of the deasphalted oil under first effective hydroprocessingconditions to form a hydroprocessed effluent, the at least a portion ofthe deasphalted oil having a kinematic viscosity at 100° C. of at least30 cSt, the hydroprocessed effluent having a sulfur content of 50 wppmor less and anitrogen content of 20 wppm or less, the first effectivehydroprocessing conditions comprising a first amount of conversion ofthe at least a portion of the deasphalted oil relative to 370° C.;separating the hydroprocessed effluent to form at least a fractioncomprising fuels boiling range portion and a hydroprocessed bottomsfraction; and hydroprocessing at least a portion of the hydroprocessedbottoms fraction under second effective hydroprocessing conditions toform a catalytically dewaxed effluent, the second effectivehydroprocessing conditions comprising catalytic dewaxing conditions andfurther comprising a second amount of conversion of the at least aportion of the hydroprocessed bottoms fraction, a yield of a 370° C.+portion of the catalytically dewaxed effluent being at least about 50 wt% relative to the at least a portion of the deasphalted oil. wherein the370° C.+ portion of the catalytically dewaxed effluent comprises a VI ofat least 100, a pour point of −10° C. or less, and akinematic viscosityat 100° C. of 8 cSt to 20 cSt.
 9. The method of claim 8, wherein the370° C.+ portion of the catalytically dewaxed effluent comprises asaturates content of at least 90 wt %.
 10. The method of claim 8,wherein the 370° C.+ portion of the catalytically dewaxed effluent has apour point of −15° C. or less.
 11. The method of claim 8, wherein thethe 370° C.+ portion of catalytically dewaxed effluent has a VI of atleast
 110. 12. The method of claim 8, wherein the first effectivehydroprocessing conditions comprising conditions for conversion of 7 wt% to 25 wt % of the at least a portion of the deasphalted oil relativeto a conversion temperature of 370° C., the second effectivehydroprocessing conditions comprising conditions for conversion of 10 wt% to 20 wt % of the at least a portion of the hydroprocessed bottoms.13. The method of claim 12, wherein the second effective hydroprocessingconditions further comprise a) second hydrotreating conditions in thepresence of a noble metal hydrotreating catalyst, b) secondhydrocracking conditions in the presence of a noble metal hydrocrackingcatalyst, or c) a combination thereof.
 14. The method of claim 8,wherein the second effective hydroprocessing conditions further comprisesecond aromatic saturation conditions in the presence of a noble metalaromatic saturation catalyst.
 15. The method of claim 8, furthercomprising separating the catalytically dewaxed effluent underseparation conditions comprising a pressure of at least 90 kPaa to forma 370° C.+ portion, the separating the hydroprocessed effluentcomprising separating the hydroprocessed effluent under separationconditions comprising a pressure of at least 90 kPaa.
 16. A lubricantcomposition having a T5 boiling point of at least 350° C., a T30 boilingpoint of 427° C. or less, and a T90 boiling point of at least 566° C.,the lubricant composition comprising a sulfur content of 50 wppm or less(or 20 wppm or less), a nitrogen content of 20 wppm or less, a saturatescontent of at least 90 wt %, a VI of at least 100, and pour point of−10° C. or less, and a kinematic viscosity at 100° C. of 8 cSt to 20cSt.
 17. The lubricant composition of claim 16, wherein the kinematicviscosity at 100° C. is 8 cSt to 18 cSt.
 18. The lubricant compositionof claim 16, wherein the lubricant composition has a pour point of −15°C. or less.
 19. The lubricant composition of claim 16, wherein thelubricant composition has a VI of at least
 110. 20. The lubricantcomposition of claim 16, wherein the lubricant composition furthercomprises an additive.